CN105722896B

CN105722896B - The manufacturing method of fibre reinforced polyarylene sulfide

Info

Publication number: CN105722896B
Application number: CN201480059203.6A
Authority: CN
Inventors: 今井直吉; 佐野健太郎; 猪濑启介
Original assignee: Toray Industries Inc
Current assignee: Toray Industries Inc
Priority date: 2013-10-29
Filing date: 2014-10-24
Publication date: 2018-12-28
Anticipated expiration: 2034-10-24
Also published as: TWI648343B; KR20160079805A; EP3064535B1; CN105722896A; US10017613B2; EP3064535A4; JP5768943B1; TW201527431A; WO2015064484A1; EP3064535A1; US20160257793A1; JPWO2015064484A1

Abstract

The present invention relates to using polyarylene sulfide and poly- carbodiimide as raw material come after obtaining poly- carbodiimide modified polyarylene sulfide, make resulting poly- carbodiimide modified polyarylene sulfide melting, with carbon fiber with special ratios carry out Composite and complex is made, the fibre reinforced polyarylene sulfide for having both mechanical characteristic and molding cycles is manufactured well so as to productivity.

Description

The manufacturing method of fibre reinforced polyarylene sulfide

Technical field

The present invention relates to manufacture the fibre reinforced for having both mechanical characteristic and molding cycles well for productivity to gather The method of arylene sulfide.

Background technique

Fibre reinforced composites comprising thermoplastic resin and reinforcing fiber have the feature that performance thermoplastic resin Characteristic and form handling ease, or the excellent such feature of recycling property.It is public as such fibre reinforced composites What is known is that the thermoplasticity prepreg arranged with making reinforcing fiber sheet, the particle for making reinforcing fiber random dispersion etc. are varied Moulding material form.Fibre reinforced composites are widely used as due to the balancing good of light weight and mechanical characteristic The industrial materials of structure component, casting of electronic device, sport-utility, the building materials of aircraft, automobile, ship etc. etc..

Polyarylene sulfide heat resistance, chemical resistance are especially excellent in thermoplastic resin, can expect it is fine with enhancing The fiber reinforcement polyarylene sulfide of Composite is tieed up to the development of substitution on the way of metal material.However, as metal material Substitution, in terms of developing fiber reinforcement polyarylene sulfide, further increasing for mechanical characteristic, especially tensile strength is to ask Topic.This is because the tensile elongation of general polyarylene sulfide than reinforcing fiber tensile elongation (for example, if being carbon fiber Dimension is then 2% or so) it is low, therefore do not play the reinforcing effect of reinforcing fiber to the greatest extent fully.

As one of the method for improving the tensile strength of fiber reinforcement polyarylene sulfide, polyarylene sulfide used can be enumerated The high elongation rate of ether.However, the tensile elongation of polyarylene sulfide is with its molecular weight and then melt viscosity has correlativity, If improving the tensile elongation of polyarylene sulfide, there is melt viscosity also to will increase, becomes with the Composite of reinforcing fiber It is difficult.Further, in this case, due to technological temperature be also required to it is at higher temperature, for be easy productivity well It is unsuitable for manufacture fiber reinforcement polyarylene sulfide.Therefore fiber reinforcement polyarylene sulfide tensile strength raising with It is productive to take into account as important technical task.

As the another method for improving the tensile strength of fiber reinforcement polyarylene sulfide, it can enumerate and be carried out using additive Modification.However, in general fusing point is 285 DEG C or so to polyarylene sulfide, in high range in thermoplastic resin, Additive dissolution (the also referred to as exudation (bleed out) or leakage in the processing and forming of fiber reinforcement polyarylene sulfide (bleed)), there are problems that polluting molding die.In order to obtain the excellent molded product of exterior quality, need periodically to remove mold Pollution become the problem of substantially damaging molding cycles therefore in this case.

Based on these reasons, the productivity when raising of the mechanical characteristic of fiber reinforcement polyarylene sulfide is manufactured with it is had both Become important technical task with molding cycles when processing and forming.

The fibre reinforced thermoplastic comprising carbon fiber Yu thermoplastic resin and carbodiimide reagent is disclosed in patent document 1 Property resin.Although however, describe the application of polyarylene sulfide in the specification of patent document 1, be not disclosed about in The method of control exudation when processing and forming at high temperature, as carbodiimide reagent, having used only has a carbon in 1 molecule The compound of di-imidogen, they are the additives for being easy to dissolve out from fibre reinforced thermoplastic resin, therefore cannot inhibit fine Exudation of the dimension enhancing polyarylene sulfide in processing and forming.

The resin combination comprising polyphenylene sulfide and poly- carbodiimide is disclosed in patent document 2.It is disclosed in patent document 2 Polyphenylene sulfide and poly- carbodiimide are subjected to melting mixing and the technology of modified polyphenyl thioether is made, although disclosing using carbon The reinforcing fibers such as fiber, but be not disclosed about in the method for the exudation for controlling poly- carbodiimide in processing and forming, it cannot press down The exudation when processing and forming of fiber reinforcement polyarylene sulfide processed, when processing and forming as fiber reinforcement polyarylene sulfide at Type cyclicity is insufficient.

The resin of material is disclosed comprising polyarylene sulfide and aliphatic poly carbodiimide system's resin and filled in patent document 3 Composition, as control processing and forming when as mold fouling the reason of exudation method, only disclose aliphatic poly carbon two The additive amount of imines system resin, it is also no open for the degree of mold fouling, it is poly- still cannot to be adequately suppressed fiber reinforcement The exudation when processing and forming of arylene sulfide, molding cycles when processing and forming as fiber reinforcement polyarylene sulfide are not Adequately.

The reinforcing material being surface-treated with carbodiimide compound is disclosed in patent document 4 and has used the reinforcement The composite wood of material, but without using illustration of the polyarylene sulfide as matrix resin, further also add without open control molding The method that working hour becomes the exudation of the reason of mold fouling, therefore the molding of fiber reinforcement polyarylene sulfide cannot be adequately suppressed Exudation when processing, molding cycles when processing and forming as fiber reinforcement polyarylene sulfide are insufficient.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Publication 5-156081 bulletin

Patent document 2: Japanese Unexamined Patent Publication 5-86291 bulletin

Patent document 3: Japanese Unexamined Patent Publication 10-273593 bulletin

Patent document 4: Japanese Unexamined Patent Publication 8-59303 bulletin

Summary of the invention

Problems to be solved by the invention

The present invention attempts the problem of improving such conventional art, and project is to provide when can inhibit processing and forming Exudation, productivity manufacture the method for having both the fibre reinforced polyarylene sulfide of mechanical characteristic and molding cycles well.

The method used for solving the problem

Inventors etc. have made intensive studies in order to solve the above problems, as a result, it has been found that by via specific manufacture work Sequence manufactures the fibre reinforced polyarylene sulfide for having both mechanical characteristic and molding cycles so as to productivity well, by This completes the present invention.

The present invention in order to solve the above problems, has any composition of following (1)~(3).

(1) a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following process (I-1)~(III-1).

Process (I-1): will there is the above carbodiimide of at least two in 100 mass parts of polyarylene sulfide (A) and 1 molecule 0.1~10 mass parts of poly- carbodiimide (B) mixed, resulting mixture heat and melting mixing, to obtain The process for obtaining melting mixing object

Process (II-1): will by process (I-1) obtain melting mixing object polyarylene sulfide (A) glass transition temperature Du or more and fusing point temperature below heated, to promote the reaction of the carbodiimide in melting mixing object and obtain The process of poly- carbodiimide modified polyarylene sulfide (C-1)

Process (III-1): making poly- carbodiimide modified polyarylene sulfide (C-1) melting obtained by process (II-1), with It is carbon fiber (D) Composite of 10~300 mass parts, the process for obtaining complex relative to 100 mass parts of polyarylene sulfide (A)

(2) a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following process (I-2)~(III-2).

Process (I-2): by the poly- carbodiimide (B) in 1 molecule with the above carbodiimide of at least two in the ingredient (B) temperature more than softening point is heated, to promote the mutual reaction of carbodiimide and to obtain poly- carbodiimide anti- The process for answering object (B-2)

Process (II-2): by 100 mass parts of polyarylene sulfide (A) and above-mentioned poly- carbodiimide reactant (B-2) 0.1~10 Mass parts are mixed, and heat simultaneously melting mixing for resulting mixture, to obtain poly- carbodiimide modified polyarylene The process of thioether (C-2)

Process (III-2): making poly- carbodiimide modified polyarylene sulfide (C-2) melting obtained by process (II-2), with It is carbon fiber (D) Composite of 10~300 mass parts, the process for obtaining complex relative to 100 mass parts of polyarylene sulfide (A)

(3) a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following process (I-3)~(III-3).

Process (I-3): acquisition, which is mixed in 100 mass parts of polyarylene sulfide (A) and 1 molecule, has the above carbon of at least two The process of the mixture of 0.1~10 mass parts of poly- carbodiimide (B) of di-imidogen

Process (II-3): will by temperature of the mixture more than the fusing point of polyarylene sulfide (A) that process (I-3) is obtained into Row heating and melting mixing, to promote the reaction of carbodiimide and obtain poly- carbodiimide modified polyarylene sulfide (C-3) Process

Process (III-3): the temperature temperature below when melting mixing in process (II-3) keeps above-mentioned poly- carbon two sub- Amine modified polyarylene sulfide (C-3) melting, with the carbon fiber for relative to 100 mass parts of polyarylene sulfide (A) being 10~300 mass parts Tie up (D) Composite, the process for obtaining complex

The effect of invention

By the invention it is possible to exudation when inhibiting processing and forming, being able to produce property manufactures have both mechanical characteristic well With the fibre reinforced polyarylene sulfide of molding cycles.

Specific embodiment

The manufacturing method for the 1st fibre reinforced polyarylene sulfide that one embodiment of the present invention is related to include (I-1)~ (III-1) process.Firstly, the process of (I-1)~(III-1) employed in the 1st manufacturing method is described in more detail.

< process (I-1) >

Process (I-1) is to mix polyarylene sulfide (A) with poly- carbodiimide (B), and resulting mixture is carried out Simultaneously melting mixing is heated, thus the process for obtaining melting mixing object.

In process (I-1), about the method for obtaining mixture, from making polyarylene sulfide (A) and poly- carbodiimide (B) to the greatest extent From the perspective of may equably mixing, may be exemplified by granular polyarylene sulfide (A) and granular poly- carbodiimide (B) into The method of row dry type blending.As the device for carrying out dry type blending, it may be exemplified Henschel mixer, wave mixing machine Deng.Furthermore it is preferred that atmosphere when obtaining mixture carries out under non-oxidizing atmosphere, it is also preferred that being performed under reduced pressure.Institute Call non-oxidizing atmosphere, refer to the oxygen concentration in gas phase that mixture is contacted be 5 volume % hereinafter, preferably 2 volume % with Under, further preferably it is substantially free of the atmosphere of oxygen, the i.e. non-active gas atmospheres such as nitrogen, helium, argon gas, wherein especially It is the easiness aspect from economy and operation, preferably nitrogen atmosphere.By using such mixed method, thus Before carrying out following melting mixing, the reduction of the reactivity of polyarylene sulfide (A) and poly- carbodiimide (B) can inhibit, therefore It is preferred that.

The number average bead diameter for carrying out polyarylene sulfide (A) and poly- carbodiimide (B) when dry type blending is preferably 0.001~ 10mm, more preferably 0.01~5mm, further preferably 0.1~3mm.In addition, polyarylene sulfide (A) and poly- carbodiimide (B) The value of respective number average bead diameter is closer to the more preferred.By becoming the range of such number average bead diameter, can reduce in mixture Interior separation, therefore preferably.

In the mixture of process (I-1), poly- carbodiimide (B) is contained relative to 100 mass parts of polyarylene sulfide (A) 0.1~10 mass parts are necessary, and preferably comprise 0.1~5 mass parts.Poly- carbodiimide (B) containing ratio less than 0.1 mass When part, the amount of poly- carbodiimide (B) is insufficient, does not show mentioning for the mechanical characteristic of resulting fibre reinforced polyarylene sulfide High effect.In addition, if the containing ratio of poly- carbodiimide (B) is more than 10 mass parts, then on the contrary poly- carbodiimide (B) excessively, Therefore the mechanical characteristic of resulting fibre reinforced polyarylene sulfide reduces.

In process (I-1), the purpose for carrying out melting mixing is, by making polyarylene sulfide (A) and poly- carbodiimide (B) Temperature more than their fusing point is heated and melts them, is kneaded under melting condition, to make polyarylene Functional group possessed by thioether (A) is reacted with carbodiimide possessed by poly- carbodiimide (B).Poly- carbodiimide (B) In 1 molecule there is the above carbodiimide of at least two to be necessary.For only having 1 carbodiimide in 1 molecule Single carbon diimine (B '), polyarylene sulfide (A) and unreacted single carbon diimine (B ') become excess quantity, and resulting carbon fiber increases The molding cycles of strong polyarylene sulfide reduce.

As for carrying out the device of melting mixing, may be exemplified in process (I-1) Labo Plastomill mixing machine, Extruder.Labo Plastomill mixing machine is to put into the raw material of specified amount to mixing machine, and it is mixed to carry out certain time melting The device of refining, easily controllable melting mixing time.Extruder is that the raw material continuously put into is carried out to melting mixing while conveying simultaneously The productivity of the device of discharge, melting mixing object is excellent.

As extruder used in melting mixing in process (I-1), single axle extruding machine, biaxial extruder may be exemplified, Biaxial extruder that wherein can be excellent it is preferable to use melting and mixing.As biaxial extruder, may be exemplified spiro rod length with The biaxial extruder that the ratio between screw diameter (spiro rod length)/(screw diameter) is 20~100.Further, the spiral shell of biaxial extruder Bar combination whole process, the length of kneading disk etc., the different screw portion of features of shape and constitute, from melting and mixing and reactive It improves aspect to set out, preferably comprises 1 or more kneading disk.

Further, its at least part is preferably performed under reduced pressure by the melting mixing in process (I-1).As subtracting Side of the region using Labo Plastomill mixing machine preferably to cover melting mixing object entirety under the conditions of pressure Formula is configured, using extruder, be preferably provided at the position (spiro rod length) of distance discharge melting mixing object/ (screw diameter) is the position in front of 0~10.As become such reduced pressure under region in degree of decompression standard, with Gauge pressure meter is preferably -0.05MPa hereinafter, more preferably -0.08MPa or less.Here so-called gauge pressure, being will be big using vacuum meter Air pressure is set as the degree of decompression that 0MPa is measured.By carrying out melting mixing under such reduced pressure, so as to The ingredient that polyarylene sulfide (A), the pyrolysate of poly- carbodiimide (B) etc. are easy to volatilize is reduced, the carbon fiber of acquisition can be improved The molding cycles of dimension enhancing polyarylene sulfide, therefore preferably.

As the temperature for carrying out melting mixing in process (I-1), preferably 285~400 DEG C, more preferably 285~350 ℃.If the temperature for carrying out melting mixing is higher than such range, polyarylene sulfide (A), poly- carbodiimide (B) can warm sometimes It decomposes, mechanical characteristic, the molding cycles of resulting fibre reinforced polyarylene sulfide reduce.If carrying out the temperature of melting mixing Degree is lower than such range, then polyarylene sulfide (A) does not melt sometimes, cannot get melting mixing object.

It is preferably 0.5~30 minute that the time of melting mixing is carried out in process (I-1), and more preferably 0.5~15 minute, into One step is preferably 0.5~10 minute, and particularly preferably 0.5~5 minute.It is longer than such range in the time for carrying out melting mixing In the case where, polyarylene sulfide (A) can be crosslinked sometimes, thickening, the Composite change with carbon fiber (D) in process (III-1) It obtains difficult.In the case where carrying out time shorter than such range of melting mixing, polyarylene sulfide (A), poly- carbon two are sub- sometimes Amine (B) does not melt, and cannot get melting mixing object.

In process (I-1), if will be since heating mixture up to polyarylene sulfide (A) and poly- carbodiimide (B) Time required for melting terminates is set as t1 (second), will terminate from polyarylene sulfide (A) and poly- carbodiimide (B) melting up to taking The time required for melting mixing object is set as t2 (second) out, then preferred t1 < t2.By being set as such condition, so as to make Functional group possessed by polyarylene sulfide (A) further increases with reacting for carbodiimide possessed by poly- carbodiimide (B). It, can example in the case that the melting mixing in process (I-1) uses Labo Plastomill mixing machine about t1 here Show from by mixture and put into mixing machine up to suitably taking out a part of melting mixing object, and polyarylene sulfide can be confirmed (A) and the time required for the melting of poly- carbodiimide (B).In addition, t2 can be by straight to mixing machine from putting into mixture T1 is removed in the time to required for taking out and is found out.

< process (II-1) >

Process (II-1) be will by process (I-1) obtain melting mixing object polyarylene sulfide (A) glass transition More than temperature and fusing point temperature below is heated, to promote the reaction of the carbodiimide in melting mixing object and obtain The process for obtaining poly- carbodiimide modified polyarylene sulfide (C-1).

Here the reaction of the carbodiimide in so-called melting mixing object refers to following reactions (1) and (2).

It reacts (1): functional group possessed by polyarylene sulfide (A) and carbodiimide possessed by poly- carbodiimide (B) Reaction

React (2): carbodiimide possessed by poly- carbodiimide (B) is reacted each other and forms dimer or trimerization Body, poly- carbodiimide (B) form the reaction of cross-linked structure

Therefore, as poly- carbodiimide modified polyarylene sulfide (C-1), may be exemplified comprising poly- carbodiimide (B) with The island phase island structure comprising poly- carbodiimide (B), island knot are dispersed in the marine facies of the reactant of polyarylene sulfide (A) Structure further has to form part or all of structure being crosslinked by reacting (2) of island phase poly- carbodiimide (B).It is logical It crosses using such structure, so as to expect that poly- carbodiimide (B) is difficult to seep from resulting fibre reinforced polyarylene sulfide Effect out.

In process (II-1), it will be turned by the melting mixing object that process (I-1) is obtained in the vitrifying of polyarylene sulfide (A) More than temperature and purpose that fusing point temperature below is heated is, passes through and polyarylene sulfide (A) is inhibited itself to be crosslinked Reaction, while improving reaction (1) and reacting the reactivity of (2), to reduce poly- carbodiimide (B) from resulting fibre reinforced It is oozed out in polyarylene sulfide.Especially since poly- carbodiimide (B) has the above carbodiimide of at least two in 1 molecule, Therefore it can expect the effect that exudation is become difficult to because of reaction (2).

In process (II-1), as will by process (I-1) obtain melting mixing object polyarylene sulfide (A) glass Change transition temperature or more and the method that is heated of fusing point temperature below, may be exemplified following methods: will be by process (I-1) The melting mixing object of acquisition is directly transferred to pressure forming machine, the method for heating pressurization slabbing in the molten state；It will be by work After graininess is made in the melting mixing object that sequence (I-1) obtains, it is transferred to the method that baking oven is heated.

As more than the glass transition temperature of the polyarylene sulfide (A) in process (II-1) and fusing point temperature below Degree, may be exemplified 90~280 DEG C, from the viewpoint of improving above-mentioned reaction (1) and reacting the reactivity of (2), further preferably It is 200~260 DEG C.In addition, differential scanning calorimetry (DSC) can be used in the glass transition temperature and fusing point of polyarylene sulfide (A) (DSC) it finds out.

It is carried out in process (II-1) as more than the glass transition temperature of polyarylene sulfide (A) and below fusing point The time of heating, preferably 5~720 minutes, more preferably 20~360 minutes, further preferably 30~180 minutes.Into Row is compared with such range in the case where prolonged heating, and polyarylene sulfide (A) can be crosslinked sometimes, thickening, process (III- 1) being become difficult with the Composite of carbon fiber (D) in.For the heating of short time compared with such range, have Shi Fanying (1) and the reactivity for reacting (2) become inadequate, the molding cycles drop of resulting fibre reinforced polyarylene sulfide It is low.

It is heated more than the glass transition temperature of polyarylene sulfide (A) and below fusing point in process (II-1) When atmosphere preferably carried out under non-oxidizing atmosphere, it is also preferred that being performed under reduced pressure.So-called non-oxidizing atmosphere, refers to The oxygen concentration in gas phase that mixture is contacted is 5 volume % hereinafter, preferably 2 volume % are hereinafter, further preferably substantive Upper oxygen-free atmosphere, the i.e. non-active gas atmospheres such as nitrogen, helium, argon gas, wherein from the easiness side of economy and operation Face is set out, particularly preferably nitrogen atmosphere.By being set as such atmosphere, the crosslinking of polyarylene sulfide (A) itself can be inhibited.

< process (III-1) >

Process (III-1) is poly- carbodiimide modified polyarylene sulfide (C-1) melting for making to be obtained by process (II-1), with Carbon fiber (D) Composite and the process for obtaining complex.

In process (III-1), the carbon fiber (D) of Composite relative to 100 mass parts of polyarylene sulfide (A) be 10~ 300 mass parts are necessary, preferably 10~200 mass parts, more preferably 20~100 mass parts, further preferably 20~ 50 mass parts.When the containing ratio of carbon fiber (D) is less than 10 mass parts, the amount of carbon fiber (D) is insufficient, does not show resulting The improvement effect of the mechanical characteristic of fibre reinforced polyarylene sulfide.If the containing ratio of carbon fiber (D) is more than 300 mass parts, Become difficult poly- carbodiimide modified polyarylene sulfide (C-1) with carbon fiber (D) Composite, the carbon fiber as a result obtained increases The mechanical characteristic of strong polyarylene sulfide reduces.

In process (III-1), as making poly- carbodiimide modified polyarylene sulfide (C-1) and carbon fiber (D) Composite Method, may be exemplified following methods: being impregnated in the poly- carbodiimide modified polyarylene sulfide (C-1) of melting aftermentioned such The method of substrate comprising carbon fiber (D)；Using extruder by poly- carbodiimide modified polyarylene sulfide (C-1) and carbon fiber (D) method etc. of melting mixing is carried out.

In process (III-1), as make melting poly- carbodiimide modified polyarylene sulfide (C-1) be impregnated in comprising carbon The method of the substrate of fiber (D), may further illustrate will be pre-machined the poly- carbodiimide modified polyarylene sulfide of slabbing (C-1) lamination is carried out with the substrate comprising carbon fiber (D), the method for being carried out heating pressurization using pressure forming machine.

In process (III-1), as the temperature for making poly- carbodiimide modified polyarylene sulfide (C-1) melting, preferably 285~400 DEG C, more preferably 285~350 DEG C.If the temperature of melting is higher than such range, sometimes polyarylene sulfide (A), poly- carbodiimide (B) can thermally decompose, the mechanical characteristic of resulting fibre reinforced polyarylene sulfide, molding cycles drop It is low.If the temperature of melting is lower than such range, poly- carbodiimide modified polyarylene sulfide (C-1) is not melted sometimes, obtains Less than complex.

In process (III-1), as compound up to obtaining from poly- carbodiimide modified polyarylene sulfide (C-1) is melted Time required for body, preferably 1~120 minute, more preferably 1~30 minute, further preferably 1~10 minute.Pass through It is set as in such range, so that productivity obtains fibre reinforced polyarylene sulfide well.

The manufacturing method for the 2nd fibre reinforced polyarylene sulfide that one embodiment of the present invention is related to include (I-2)~ (III-2) process.The process of (I-2)~(III-2) used by 2nd manufacturing method is illustrated in further detail.

< process (I-2) >

Process (I-2) is by the poly- carbodiimide (B) in 1 molecule with the above carbodiimide of at least two in the ingredient (B) temperature more than softening point is heated, to promote the mutual reaction of carbodiimide and to obtain poly- carbodiimide anti- The process for answering object (B-2).

Here the mutual reaction of so-called carbodiimide, be carbodiimide possessed by poly- carbodiimide (B) each other It reacts and forms dimer or tripolymer, polymerize as poly- carbodiimide (B), carry out the reaction of molecular weight. Poly- carbodiimide reactant (B-2) has following effects: being improved by molecular weight heat resistance, from resulting fibre reinforced The ingredient that polyarylene sulfide is easy to ooze out can reduce.

It is excellent from the viewpoint of productivity as the method for heating poly- carbodiimide (B) in process (I-2) It is sub- to may be exemplified the poly- carbon two that will be added to the container for the method for being selected as disposably heating poly- carbodiimide (B) in large quantities The method that amine (B) is heated in baking oven.By disposably heating poly- carbodiimide (B) in large quantities, so that productivity is good Poly- carbodiimide reactant (B-2) is obtained well.Further by using poly- carbodiimide reactant (B-2), thus under having State effect: the heating time in process compared with process (I-2) rearward can shorten, the life of fibre reinforced polyarylene sulfide Production property is excellent.

In process (I-2), so-called baking oven refers to the air by heat or is generated by wall surface, the heating source in furnace Radiant heat heat the device of the mechanism of content, may be exemplified hot-air oven, vacuum drying oven, electric furnace etc..In an oven, from Temperature in easily controllable furnace inhibited from the perspective of heating up, it is preferable to use hot-air oven, vacuum drying oven.

In addition, atmosphere when poly- carbodiimide (B) is heated preferably carries out under non-oxidizing atmosphere, it is also preferred that It is carried out under reduced pressure.So-called non-oxidizing atmosphere refers to that poly- carbodiimide (B), poly- carbodiimide reactant (B-2) are contacted Gas phase in oxygen concentration be 5 volume % hereinafter, preferably 2 volume % are hereinafter, be further preferably substantially free of the gas of oxygen The non-active gas atmospheres such as atmosphere, i.e. nitrogen, helium, argon gas, wherein from the easiness aspect of economy and operation, especially Preferably nitrogen atmosphere.In the case where being set as under reduced pressure, as the standard of degree of decompression, be preferably in terms of gauge pressure- 0.05MPa is hereinafter, more preferably -0.08MPa or less.Here so-called gauge pressure is that atmospheric pressure is set as 0MPa using vacuum meter The degree of decompression being measured.By being heated in such a situa-tion, so as to inhibit poly- carbodiimide (B), gather Oxidation, the thermal decomposition of carbodiimide reactant (B-2), the mechanical characteristic of resulting fibre reinforced polyarylene sulfide, molding follow Ring can be improved, therefore preferably.

Temperature more than softening point in process (I-2) as poly- carbodiimide (B), may be exemplified 50~250 DEG C.Into Temperature when one step is heated poly- carbodiimide (B) in process (I-2) is more preferably 70~250 DEG C, further preferably It is 100~150 DEG C.By in the range that keeps the temperature heated such, thus resulting poly- carbodiimide reactant (B- 2) in, structure made of carbodiimide reacts with each other coexists with unreacted carbodiimide, and resulting fibre reinforced is poly- Mechanical characteristic, the molding cycles of arylene sulfide can be improved.In addition, heat engine can be used in the softening point of poly- carbodiimide (B) Tool analytical equipment (TMA) and find out.

It by the time that poly- carbodiimide (B) heats is preferably 1~48 hour in process (I-2), more preferably 2~ 30 hours, further preferably 3~24 hours.In the case where the time heated being longer than such range, poly- carbon sometimes Unreacted carbodiimide in diimine reactant (B-2) is few, and the mechanics of resulting fibre reinforced polyarylene sulfide is special Property cannot improve.In the case where the time heated shorter than such range, carbodiimide has been reacted with each other sometimes Structure is few, and the molding cycles of resulting fibre reinforced polyarylene sulfide cannot improve.

In process (I-2), in order to obtain poly- carbodiimide reactant (B-2), using in 1 molecule have at least two with The poly- carbodiimide (B) of upper carbodiimide is necessary.For only the single carbon two with 1 carbodiimide is sub- in 1 molecule Amine (B ') is unable to molecular weight, therefore the raising of heat resistance even if reacting with each other carbodiimide can not be polymerize Effect is small.Further, carbodiimide is not residual in reactant obtained by the carbodiimide of single carbon diimine (B ') reacts with each other It deposits.Therefore, even if reactant obtained by reacting with each other using the carbodiimide of single carbon diimine (B '), gained can not be had both Fibre reinforced polyarylene sulfide mechanical characteristic improvement effect and molding cycles.

< process (II-2) >

Process (II-2) is to react 100 mass parts of polyarylene sulfide (A) with the poly- carbodiimide obtained by process (I-2) 0.1~10 mass parts of object (B-2) are mixed, and heat simultaneously melting mixing for resulting mixture, to obtain poly- carbon two The process of imine modified polyarylene sulfide (C-2).

In process (II-2), about the method for obtaining mixture, from reacting polyarylene sulfide (A) with poly- carbodiimide From the perspective of object (B-2) mixes as homogeneously as possible, it may be exemplified granular polyarylene sulfide (A) and granular poly- carbon two The method of imine reaction object (B-2) progress dry type blending.As the device for carrying out dry type blending, it is mixed to may be exemplified Henschel Conjunction machine waves mixing machine etc..Furthermore it is preferred that atmosphere when obtaining mixture carries out under non-oxidizing atmosphere, it is also preferred that subtracting It is carried out under the conditions of pressure.So-called non-oxidizing atmosphere, refer to the oxygen concentration in gas phase that mixture is contacted be 5 volume % hereinafter, Preferably 2 volume % are hereinafter, be further preferably substantially free of the atmosphere of oxygen, the i.e. non-active gas such as nitrogen, helium, argon gas Atmosphere, wherein from the easiness aspect of economy and operation, particularly preferably nitrogen atmosphere.By using such mixed Conjunction method, to can inhibit polyarylene sulfide (A) and poly- carbodiimide reactant (B-2) before carrying out following melting mixing Reactivity reduction, therefore preferably.

Polyarylene sulfide (A) and the number average bead diameter of poly- carbodiimide reactant (B-2) when carrying out dry type blending are preferably 0.001~10mm, more preferably 0.01~5mm, further preferably 0.1~3mm.In addition, polyarylene sulfide (A) and poly- carbon two The value of imine reaction object (B-2) respective number average bead diameter is closer to the more preferred.It, can by becoming the range of such number average bead diameter To reduce the separation in mixture, therefore preferably.

In the mixture of process (II-2), poly- carbodiimide reactant (B-2) is relative to 100 matter of polyarylene sulfide (A) Amount part is contained 0.1~10 mass parts and is necessary, and 0.1~5 mass parts are preferably comprised.In poly- carbodiimide reactant (B-2) When containing ratio is less than 0.1 mass parts, the amount of poly- carbodiimide reactant (B-2) is insufficient, does not show resulting carbon fiber and increases The improvement effect of the mechanical characteristic of strong polyarylene sulfide.In addition, if the containing ratio of poly- carbodiimide reactant (B-2) is more than 10 Mass parts, then on the contrary poly- carbodiimide reactant (B-2) excessively, therefore the mechanics of resulting fibre reinforced polyarylene sulfide Characteristic reduces.

In process (II-2), the purpose for carrying out melting mixing is, by making temperature of the polyarylene sulfide (A) more than fusing point Degree is heated and makes its melting, is mixed under the melting condition of polyarylene sulfide (A) with poly- carbodiimide reactant (B-2) Refining, to make carbodiimide possessed by functional group possessed by polyarylene sulfide (A) and poly- carbodiimide reactant (B-2) It is reacted and obtains poly- carbodiimide modified polyarylene sulfide (C-2).By becoming such state, can have both resulting The raising of the mechanical characteristic of fibre reinforced polyarylene sulfide and molding cycles.

As the device for carrying out melting mixing in process (II-2), Labo Plastomill mixing may be exemplified Machine, extruder.Labo Plastomill mixing machine is to put into the raw material of specified amount to mixing machine, and it is molten to carry out certain time Melt the device of mixing, easily controllable melting mixing time.Extruder is that the raw material continuously put into progress melting mixing is defeated simultaneously The productivity of the device for sending and being discharged, melting mixing object is excellent.

As extruder used in melting mixing in process (II-2), single axle extruding machine may be exemplified, twin shaft squeezes out Machine, wherein biaxial extruder that can be excellent it is preferable to use melting and mixing.As biaxial extruder, spiro rod length may be exemplified The biaxial extruder for being 20~100 with the ratio between screw diameter (spiro rod length)/(screw diameter).Further, biaxial extruder Length, the different screw portion of features of shape of screw combinations whole process, kneading disk etc. and constitute, from melting and mixing and reactivity Raising in terms of set out, preferably comprise 1 or more kneading disk.

Further, its at least part is preferably performed under reduced pressure by the melting mixing in process (II-2).Become Region under reduced pressure is using Labo Plastomill mixing machine preferably to cover melting mixing object entirety Mode is configured, and using extruder, being preferably provided at the position of distance discharge melting mixing object, (screw rod is long Degree)/(screw diameter) be 0~10 in front of position.Mark as the degree of decompression in the region become under such reduced pressure Standard is preferably -0.05MPa hereinafter, more preferably -0.08MPa or less in terms of gauge pressure.Here so-called gauge pressure, is using vacuum Atmospheric pressure is set as the degree of decompression that 0MPa is measured by meter.By carrying out melting mixing under such reduced pressure, from And the ingredient that polyarylene sulfide (A), the pyrolysate of poly- carbodiimide reactant (B-2) can be reduced etc. and be easy to volatilize, gained The molding cycles of fibre reinforced polyarylene sulfide can be improved, therefore preferably.

As the temperature for carrying out melting mixing in process (II-2), preferably 285~400 DEG C, more preferably 285~350 ℃.If the temperature for carrying out melting mixing is higher than such range, sometimes polyarylene sulfide (A), poly- carbodiimide reactant (B-2) it can thermally decompose, mechanical characteristic, the molding cycles of resulting fibre reinforced polyarylene sulfide reduce.If melted Melt the temperature of mixing lower than such range, then polyarylene sulfide (A) does not melt sometimes, cannot get melting mixing object.

It is preferably 0.5~30 minute that the time of melting mixing is carried out in process (II-2), and more preferably 0.5~15 minute, Further preferably 0.5~10 minute, particularly preferably 0.5~5 minute.It is longer than such model in the time for carrying out melting mixing In the case where enclosing, polyarylene sulfide (A) can be crosslinked sometimes, thickening, the Composite change with carbon fiber (D) in process (III-3) It obtains difficult.In the case where carrying out time shorter than such range of melting mixing, polyarylene sulfide (A) is not melted sometimes, obtains Less than melting mixing object.

In addition, poly- carbodiimide modified polyarylene sulfide (C-2) is led to preferably after melting mixing in process (II-2) Following methods are crossed to process slabbing, the method are as follows: be directly transferred to pressure forming machine in the molten state, heating pressurization at The method of sheet；From the method for being installed on the T-shaped mould of biaxial extruder front end, melting mixing object sheet is discharged slit die.

< process (III-2) >

Process (III-2) is poly- carbodiimide modified polyarylene sulfide (C-2) melting for making to be obtained by process (II-2), with It is carbon fiber (D) Composite of 10~300 mass parts relative to 100 mass parts of polyarylene sulfide (A), obtains the work of complex Sequence.

In process (III-2), the carbon fiber (D) of Composite relative to 100 mass parts of polyarylene sulfide (A) be 10~ 300 mass parts are necessary, preferably 10~200 mass parts, more preferably 20~100 mass parts, further preferably 20~ 50 mass parts.When the containing ratio of carbon fiber (D) is less than 10 mass parts, the amount of carbon fiber (D) is insufficient, does not show resulting The improvement effect of the mechanical characteristic of fibre reinforced polyarylene sulfide.If the containing ratio of carbon fiber (D) is more than 300 mass parts, Become difficult poly- carbodiimide modified polyarylene sulfide (C-2) with carbon fiber (D) Composite, the carbon fiber as a result obtained increases The mechanical characteristic of strong polyarylene sulfide reduces.

In process (III-2), as making poly- carbodiimide modified polyarylene sulfide (C-2) and carbon fiber (D) Composite Method, may be exemplified following methods: being impregnated in the poly- carbodiimide modified polyarylene sulfide (C-2) of melting aftermentioned such The method of substrate comprising carbon fiber (D)；Using extruder by poly- carbodiimide modified polyarylene sulfide (C-2) and carbon fiber (D) method etc. of melting mixing is carried out.

In process (III-2), as make melting poly- carbodiimide modified polyarylene sulfide (C-2) be impregnated in comprising carbon The method of the substrate of fiber (D), may further illustrate will be pre-machined the poly- carbodiimide modified polyarylene sulfide of slabbing (C-2) lamination is carried out with the substrate comprising carbon fiber (D), the method for being carried out heating pressurization using pressure forming machine.

In process (III-2), as the temperature for making poly- carbodiimide modified polyarylene sulfide (C-2) melting, preferably 285~400 DEG C, more preferably 285~350 DEG C.If the temperature of melting is higher than such range, sometimes polyarylene sulfide (A), poly- carbodiimide reactant (B-2) can thermally decompose, and the mechanical characteristic of resulting fibre reinforced polyarylene sulfide, molding follow Ring reduces.If the temperature of melting is lower than such range, poly- carbodiimide modified polyarylene sulfide (C-2) is not melted sometimes Melt, cannot get complex.

In process (III-2), as compound up to obtaining from poly- carbodiimide modified polyarylene sulfide (C-2) is melted Time required for body, preferably 1~120 minute, more preferably 1~30 minute, further preferably 1~10 minute.Pass through As in such range, fibre reinforced polyarylene sulfide can be obtained well with productivity.

The manufacturing method for the 3rd fibre reinforced polyarylene sulfide that one embodiment of the present invention is related to include (I-3)~ (III-3) process.The process of (I-3)~(III-3) used in 3rd manufacturing method is described in more detail.

< process (I-3) >

Process (I-3) is to obtain to be mixed in 100 mass parts of polyarylene sulfide (A) and 1 molecule to have the above carbon of at least two The process of the mixture of 0.1~10 mass parts of poly- carbodiimide (B) of di-imidogen.

In process (I-3), as the method for obtaining mixture, from making polyarylene sulfide (A) and poly- carbodiimide (B) to the greatest extent From the perspective of may equably mixing, may be exemplified by granular polyarylene sulfide (A) and granular poly- carbodiimide (B) into The method of row dry type blending.As the device for carrying out dry type blending, it may be exemplified Henschel mixer, wave mixing machine Deng.In addition, atmosphere when obtaining mixture preferably carries out under non-oxidizing atmosphere, it is also preferred that being performed under reduced pressure.Institute Call non-oxidizing atmosphere, refer to the oxygen concentration in gas phase that mixture is contacted be 5 volume % hereinafter, preferably 2 volume % with Under, further preferably it is substantially free of the atmosphere of oxygen, the i.e. non-active gas atmospheres such as nitrogen, helium, argon gas, wherein from warp It sets out in terms of Ji property and the easiness of operation, particularly preferably nitrogen atmosphere.By using such mixed method, thus into Before the following melting mixing of row, inhibit the reduction of the reactivity of polyarylene sulfide (A) and poly- carbodiimide (B), therefore preferably.

In the mixture of process (I-3), poly- carbodiimide (B) is contained relative to 100 mass parts of polyarylene sulfide (A) 0.1~10 mass parts are necessary, and preferably comprise 0.1~5 mass parts.Poly- carbodiimide (B) containing ratio less than 0.1 mass When part, the amount of poly- carbodiimide (B) is insufficient, does not show the raising of resulting fibre reinforced polyarylene sulfide mechanical characteristic Effect.In addition, if the containing ratio of poly- carbodiimide (B) is more than 10 mass parts, then on the contrary poly- carbodiimide (B) excessively, because The mechanical characteristic of this resulting fibre reinforced polyarylene sulfide reduces.

< process (II-3) >

Process (II-3) is the temperature of the mixture that will be obtained by process (I-3) more than the fusing point of polyarylene sulfide (A) Heat simultaneously melting mixing, to promote the reaction of carbodiimide and obtain poly- carbodiimide modified polyarylene sulfide (C- 3) process.

In process (II-3), it is so-called will by process (I-3) obtain mixture more than the fusing point of polyarylene sulfide (A) Temperature heat and melting mixing so as to the reaction of the carbodiimide of promotion refers to that polyarylene sulfide (A) is had Some functional groups and carbodiimide possessed by poly- carbodiimide (B) react and poly- carbodiimide (B) possessed by carbon two Imido grpup is reacted each other and forms dimer or tripolymer, and poly- carbodiimide (B) forms the reaction of cross-linked structure.

Therefore, as poly- carbodiimide modified polyarylene sulfide (C-3), may be exemplified comprising poly- carbodiimide (B) with The island phase island structure comprising poly- carbodiimide (B), island knot are dispersed in the marine facies of the reactant of polyarylene sulfide (A) Further there is structure part or all to form island phase poly- carbodiimide (B) to pass through carbon possessed by poly- carbodiimide (B) The mutual reaction of di-imidogen and the structure that has been crosslinked.By adopting such structure, so as to expect poly- carbodiimide (B) It is difficult to the effect oozed out from resulting fibre reinforced polyarylene sulfide.Especially since poly- carbodiimide (B) is in 1 molecule With the above carbodiimide of at least two, therefore is reacted with each other by carbodiimide and to form the anti-of dimer or tripolymer It answers, can expect the effect for being difficult to ooze out.For, only with the single carbon diimine (B ') of 1 carbodiimide, gathering virtue in 1 molecule Supportting thioether (A) and unreacted single carbon diimine (B ') becomes excess quantity, the molding of resulting fibre reinforced polyarylene sulfide Cyclicity reduces.

As the device for carrying out melting mixing in process (II-3), Labo Plastomill mixing may be exemplified Machine, extruder.Labo Plastomill mixing machine is to put into the raw material of specified amount to mixing machine, and it is molten to carry out certain time Melt the device of mixing, easily controllable melting mixing time.Extruder is that the raw material continuously put into progress melting mixing is defeated simultaneously The productivity of the device transported and be discharged, melting mixing object is excellent.

As extruder used in melting mixing in process (II-3), single axle extruding machine may be exemplified, twin shaft squeezes out Machine, wherein biaxial extruder that can be excellent it is preferable to use melting and mixing.As biaxial extruder, spiro rod length may be exemplified The biaxial extruder for being 20~100 with the ratio between screw diameter (spiro rod length)/(screw diameter).Further, biaxial extruder Length, the different screw portion of features of shape of screw combinations whole process, kneading disk etc. and constitute, but from melting and mixing and reaction Property raising in terms of set out, preferably comprise 1 or more kneading disk.

Further, its at least part is preferably performed under reduced pressure by the melting mixing in process (II-3).Become Region under reduced pressure is using Labo Plastomill mixing machine preferably to cover melting mixing object entirety Mode is configured, and using extruder, being preferably provided at the position of distance discharge melting mixing object, (screw rod is long Degree)/(screw diameter) be 0~10 in front of position.Mark as the degree of decompression in the region become under such reduced pressure Standard is preferably -0.05MPa hereinafter, more preferably -0.08MPa or less in terms of gauge pressure.Here so-called gauge pressure, is using vacuum Atmospheric pressure is set as the degree of decompression that 0MPa is measured by meter.By carrying out melting mixing under such reduced pressure, from And the ingredient that polyarylene sulfide (A), the pyrolysate of poly- carbodiimide (B) can be reduced etc. and be easy to volatilize, resulting carbon fiber The molding cycles of enhancing polyarylene sulfide can be improved, therefore preferably.

In process (II-3), as the temperature more than fusing point of ingredient (A), i.e., poly- carbon two is obtained by melting mixing Temperature when imine modified polyarylene sulfide (C-3), preferably 330~400 DEG C, more preferably 330~360 DEG C.By 330 DEG C or more carry out melting mixing, to carry out reacting for polyarylene sulfide (A) and poly- carbodiimide (B), poly- carbon two with the short time The productivity of imine modified polyarylene sulfide (C-3) is excellent.If the temperature for carrying out melting mixing is higher than such range, have When polyarylene sulfide (A), poly- carbodiimide (B) can thermally decompose, the mechanical characteristic of resulting fibre reinforced polyarylene sulfide, at Type cyclicity reduces.

It is preferably 0.5~30 minute that the time of melting mixing is carried out in process (II-3), and more preferably 0.5~15 point Clock, further preferably 0.5~10 minute, particularly preferably 0.5~5 minute.It is longer than in this way in the time for carrying out melting mixing Range in the case where, polyarylene sulfide (A) can be crosslinked sometimes, thickening, compound with carbon fiber (D) in process (III-3) Change becomes difficult.In the case where carrying out time shorter than such range of melting mixing, polyarylene sulfide (A), poly- carbon sometimes Diimine (B) does not melt, and cannot get melting mixing object.

In addition, poly- carbodiimide modified polyarylene sulfide (C-3) is led to preferably after melting mixing in process (II-3) Following methods are crossed to process slabbing, the method are as follows: be directly transferred to pressure forming machine in the molten state, heating pressurization at The method of sheet；From the method for being installed on the T-shaped mould of biaxial extruder front end, melting mixing object sheet is discharged slit die.

< process (III-3) >

Temperature temperature below when process (III-3) is the melting mixing in process (II-3) keeps above-mentioned poly- carbon two sub- Amine modified polyarylene sulfide (C-3) melting, with the carbon fiber for relative to 100 mass parts of polyarylene sulfide (A) being 10~300 mass parts Tie up (D) Composite, the process for obtaining complex.

In process (III-3), by the temperature process for making poly- carbodiimide modified polyarylene sulfide (C-3) melting (II-3) the temperature temperature below when melting mixing in, to can inhibit in the Composite with carbon fiber (D) by gathering The generation of the volatile ingredients in sources such as the thermal decomposition of carbodiimide modified polyarylene sulfide (C-3).When further as Composite Generated volatile ingredient can reduce, it is possible thereby to improve poly- carbodiimide modified polyarylene sulfide (C-3) and reinforcing fiber (D) closely sealed.Based on these reasons, can have both the mechanical characteristic of resulting fibre reinforced polyarylene sulfide raising and at Type cyclicity.

Further in process (III-3), temperature temperature below when as melting mixing in process (II-3), That is, temperature when melting above-mentioned poly- carbodiimide modified polyarylene sulfide (C-3), may be exemplified 280~330 DEG C, more preferably It is 280~300 DEG C.If the temperature of melting is higher than such range, for poly- carbodiimide modified polyarylene sulfide (C-3) For, mechanical characteristic, the molding cycles of the fibre reinforced polyarylene sulfide obtained sometimes because of thermal decomposition reduce.If The temperature of melting is lower than such range, then poly- carbodiimide modified polyarylene sulfide (C-3) does not melt sometimes, cannot get compound Body.

In process (III-3), as compound up to obtaining from poly- carbodiimide modified polyarylene sulfide (C-3) is melted Time required for body, preferably 1~120 minute, more preferably 1~30 minute, further preferably 1~10 minute.Pass through It is set as in such range, so that productivity obtains fibre reinforced polyarylene sulfide well.

In process (III-3), the carbon fiber (D) of Composite relative to 100 mass parts of polyarylene sulfide (A) be 10~ 300 mass parts are necessary, preferably 10~200 mass parts, more preferably 20~100 mass parts, further preferably 20~ 50 mass parts.When the containing ratio of carbon fiber (D) is less than 10 mass parts, the amount of carbon fiber (D) is insufficient, does not show resulting The improvement effect of the mechanical characteristic of fibre reinforced polyarylene sulfide.If the containing ratio of carbon fiber (D) is more than 300 mass parts, Become difficult poly- carbodiimide modified polyarylene sulfide (C-3) with carbon fiber (D) Composite, the carbon fiber as a result obtained increases The mechanical characteristic of strong polyarylene sulfide reduces.

In process (III-3), as making poly- carbodiimide modified polyarylene sulfide (C-3) and carbon fiber (D) Composite Method, may be exemplified following methods: being impregnated in the poly- carbodiimide modified polyarylene sulfide (C-3) of melting aftermentioned such The method of substrate comprising carbon fiber (D)；Using extruder by poly- carbodiimide modified polyarylene sulfide (C-3) and carbon fiber (D) method etc. of melting mixing is carried out.

In process (III-3), as make melting poly- carbodiimide modified polyarylene sulfide (C-3) be impregnated in comprising carbon The method of the substrate of fiber (D), may further illustrate: the poly- carbodiimide modified polyarylene sulfide of slabbing will be pre-machined (C-3) lamination is carried out with the substrate comprising carbon fiber (D), the method for being carried out heating pressurization using pressure forming machine.

< includes the substrate > of carbon fiber (D)

As the above-mentioned substrate comprising carbon fiber (D), it can enumerate and continuous carbon fibre (D) is arranged in one direction and is made The unidirectional array substrate of slabbing, fabric (cloth), non-woven fabrics, braided fabric, braid, silk, short linen etc..It is wherein, it is preferable to use poly- Carbodiimide modified polyarylene sulfide (C-1), (C-2) or (C-3) is relatively easy the carbon fiber (D) comprising non-woven fabric-like of impregnation Substrate.As the carbon fiber (D) of non-woven fabric-like, the preferably monofilament of carbon fiber randomly dispersed situation, such carbon The fibre length of the monofilament of fiber (D) is preferably 0.01~20mm, more preferably 0.01~10mm in terms of number average fiber length.It is logical It crosses in the range for being set as such, it is hereby achieved that the excellent fibre reinforced of mobility when mechanical characteristic and processing and forming is poly- Arylene sulfide.In addition, the fibre length of carbon fiber (D) is longer, then the mechanics of resulting poly- carbodiimide modified polyarylene sulfide Characteristic more improves.

< process (IV) >

In any manufacturing method of the invention, all preferably further include next shown in process (IV).Process (IV) for will by process (III-1), (III-2) or (III-3) obtain complex polyarylene sulfide (A) glass transition More than temperature and fusing point temperature below is heated, to promote the process of the reaction of compound intracorporal carbodiimide.

By via process (IV), can be further improved in process (II-1), (I-2), (II-2) or (II-3) into The reacting of functional group possessed by capable polyarylene sulfide (A) and carbodiimide possessed by poly- carbodiimide (B), poly- carbon two Carbodiimide possessed by imines (B) is reacted each other and forms dimer or tripolymer, and poly- carbodiimide (B), which is formed, hands over It is coupled the reactivity of the reaction of structure, it is possible to reduce polyarylene sulfide (B) is oozed out from resulting fibre reinforced polyarylene sulfide Situation.

As more than the glass transition temperature of the polyarylene sulfide (A) in process (IV) and fusing point temperature below, It may be exemplified 90~280 DEG C, further, from improving functional group possessed by above-mentioned polyarylene sulfide (A) and poly- carbodiimide (B) Carbodiimide possessed by the reaction of possessed carbodiimide and poly- carbodiimide (B) is reacted with each other and is formed Dimer or tripolymer, poly- carbodiimide (B) are formed from the perspective of the reactivity of the reaction of cross-linked structure, preferably 200~ 260℃.In addition, the glass transition temperature and fusing point of polyarylene sulfide (A) can be used differential scanning calorimetry (DSC) (DSC) and ask Out.

Added in process (IV) as more than the glass transition temperature of polyarylene sulfide (A) and below fusing point The time of heat, preferably 5~720 minutes, more preferably 20~360 minutes, further preferably 30~180 minutes.Carry out Compared with such range in the case where prolonged heating, polyarylene sulfide (A) can be crosslinked sometimes, and thickening is further heated Processing and forming becomes difficult.

< process (V) >

In any manufacturing method of the invention, all preferably further include next shown in process (V).Process (V) For the complex obtained in process (III-1), (III-2) or (III-3) or the complex that have passed through process (IV) are infused The process for penetrating molding or extrusion forming.

In process (V), as injection moulding, the method using coaxial-type screw type injection (mo(u)lding) machine may be exemplified, it can To illustrate following methods: by measuring complex in the barrel of injection (mo(u)lding) machine to become molten condition, then melting this The complex for melting state is injected in molding die, cooling, solidification, thus what the injection-molded article as defined shape took out Method.

It in process (V), as extrusion forming, may be exemplified following methods: complex added in molding die Heat is compressed and is conformed into defined shape, then, carries out cooling, solidifies, thus the side taken out as extrusion forming product Method.

Further, preferably make processing and forming temperature when injection moulding in process (V) or extrusion forming with process (III- 1) temperature when, obtaining complex in (III-2) or (III-3) is compared to be carried out under low temperature.By being set as such temperature condition, When to processing and forming in process (V), the generation of the volatile ingredient by sources such as the thermal decompositions of complex can be inhibited, at The volatile ingredient that generates can reduce when type is processed, thus in resulting molded product, can be improved ingredient (C-1), (C-2) or (C-3) closely sealed with reinforcing fiber (D), the raising and molding that can have both the mechanical characteristic of fibre reinforced polyarylene sulfide follow Ring, therefore preferably.

So-called processing and forming temperature in process (V), refer to injection (mo(u)lding) machine barrel temperature or pressure forming machine at Type mold temperature may be exemplified 280~330 DEG C, more preferably 280~300 DEG C.If the processing and forming temperature in process (V) Higher than such range, then sometimes due to the thermal decomposition of complex, and the mechanics of resulting fibre reinforced polyarylene sulfide is special Property, molding cycles reduce.If processing and forming temperature is lower than such range, it is not capable of processing complex sometimes.

It is time required for the processing and forming as complex, preferably 0.15~120 minute, more excellent in process (V) It is selected as 0.15~30 minute, further preferably 0.15~10 minute.By in the range that is set as such, so that productivity is good Ground obtains fibre reinforced polyarylene sulfide.

The manufacturing method of fibre reinforced polyarylene sulfide of the invention passes through via process (I-1)~(III-1), (I- 2)~(III-2) or (I-3)~(III-3) and the as needed process other than these processes (IV) and/or (V), from And the case where polyarylene sulfide (B) oozes out can be reduced in the state of maintaining the molding processibility of resulting complex.

Next, to as ingredient used in the present invention, polyarylene sulfide (A), poly- carbodiimide (B) and carbon fiber (D) it is illustrated.

< polyarylene sulfide (A) >

Polyarylene sulfide (A) (hereinafter, polyarylene sulfide is referred to as PAS sometimes) is with the repetitive unit of formula-(Ar-S)- As main composition unit, containing the repetitive unit be preferably 80 moles of % or more, more preferably 90 moles of % or more, into one Step is preferably the homopolymer or copolymer of 95 moles of % or more.As Ar, there is unit shown in following formula (a)~formula (k) etc. etc., Wherein it is particularly preferably unit shown in formula (a).

(R1, R2 be selected from hydrogen, the alkyl of carbon atom number 1~12, the alkoxy of carbon atom number 1~12, carbon atom number 6~ Substituent group in 24 arlydene, halogen, R1 can be the same or different with R2.)

As long as using the repetitive unit as main composition unit, so that it may comprising few shown in following formula (l)~formula (n) etc. The branching units or crosslink unit of amount.The copolymerization amount of these branching units or crosslink unit is rubbed relative to-the unit 1 of (Ar-S)- You are preferably the range of 0~1 mole of %.

In addition, PAS (A) can be the random copolymer comprising above-mentioned repetitive unit, block copolymer and their mixing Object it is any.

As the representative substance of PAS (A), polyphenylene sulfide (above-mentioned formula (a), formula (b), formula (f)~formula can be enumerated (k)), polyphenylene sulfide sulfone (above-mentioned formula (d)), polyphenylene sulfide ketone (above-mentioned formula (c)), polyphenylene sulfide ether (above-mentioned formula (e)), they Random copolymer, block copolymer and their mixture etc..As particularly preferred PAS (A), can enumerate as polymer Main composition unit contains to diphenyl sulfide unit80 moles of % or more, especially 90 moles of % Above polyphenylene sulfide (hereinafter, sometimes referred to simply as PPS)

The matter average molecular weight of PAS (A) is preferably 10,000~80,000, more preferably 10,000~60,000, further Preferably 10,000~40,000.In the case where matter average molecular weight small PAS (A), melt viscosity is low, with carbon fiber (D) Composite becomes easy, and the productivity of fibre reinforced polyarylene sulfide is excellent, therefore preferably.

In addition, the matter average molecular weight of PAS (A) can be by using generally known GPC such as size exclusion chromatographies (SEC) (gel permeation chromatography) measures.1- chloronaphthalene can be used by eluent, column temperature is set as 210 DEG C, calculates polystyrene The matter average molecular weight of conversion, so as to find out.

PAS (A) preferably has functional group in the end of main chain and/or side chain.Here so-called main chain, refers to macromolecular structure In longest chain structure part, be known as side chain from the part that main chain branch is constituted.So-called macromolecular structure refers to single The part that structural unit repeats the part of connection or multiple structural units regularly or randomly connect, so-called end refers to company Connect the last structural unit of stopping.Functional group possessed by PAS (A) is preferably the main chain and/or side chain in macromolecular structure End any one there are more than at 1, the ratio PAS with such functional group shared in PAS (A) is preferably 50 matter Measure % or more, more preferably 60 mass % or more, further preferably 80 mass % or more.By meeting such condition, from And obtain the excellent fibre reinforced polyarylene sulfide of mechanical characteristic.

As functional group possessed by PAS (A), the official that the functional group of used monomer has remained when polymerization can be used It can group；Catalyst, auxiliary agent, solvent when polymerization are introduced in end and the functional group that is formed；Macromolecular structure by thermal decomposition, Hydrolysis etc. is cut off and the functional group of formation；With the function that these functional groups are aoxidized, restore and are modified with modifying agent Group.As above-mentioned modifying agent, epichlorohydrin, polyfunctional epoxy resin, acid anhydrides etc. may be exemplified.Wherein, to macromolecular structure It destroys and is easy to control molecular weight consideration less, it is preferable to use the functional group that the functional group of used monomer has remained when polymerizeing；It is poly- Catalyst, auxiliary agent, solvent when conjunction are introduced in end and the functional group that is formed.

As functional group possessed by PAS (A), the metal of mercapto, epoxy group, carboxyl, carboxyl specifically may be exemplified Salt, amino, hydroxyl, isocyanate group,Oxazoline base, sulfonic group etc..Wherein, go out in terms of the reactivity with carbodiimide Hair, preferably mercapto, epoxy group, carboxyl, the metal salt of carboxyl, amino, hydroxyl, particularly preferably mercapto, carboxyl, ammonia Base, hydroxyl.

It is 2 mass % hereinafter, more preferably 1 mass % or less that PAS (A), which is preferably based on the oligomer extracted amount of chloroform,.This In the so-called oligomer extracted amount based on chloroform, be an index for organic oligomer synthesis point (oligomer) amount, can be by using chlorine Residual error amount when imitative 200mL extracts processing in 5 hours to PAS (A) the 10g Soxhlet of measurement calculates.By reducing in PAS (A) Oligomer ingredient, so that the carbodiimide of the functional group of the component of polymer of PAS (A) and poly- carbodiimide (B) can be more Add selective reaction, therefore obtains the excellent fibre reinforced polyarylene sulfide of molding cycles.

PAS (A) can be obtained and from polyhalo aromatic compound is reacted in polar organic solvent with vulcanizing agent Polymerization reactant, PAS (A) is recycled, is post-processed, thus to be manufactured in high yield.

So-called polyhalo aromatic compound refers to the compound in 1 molecule with 2 or more halogen atoms.As specific Example, can enumerate paracide, m-dichlorobenzene, o-dichlorohenzene, 1,3,5- trichloro-benzenes, 1,2,4- trichloro-benzenes, 1,2,4,5- tetrachlorobenzenes, Hexachloro-benzene, 2,5- dichlorotoleune, the chloro- paraxylene of 2,5- bis-, 1,4- dibromobenzene, 1,4- diiodo-benzene, 1- methoxyl group -2,5- dichloro Benzene etc..Wherein, it is preferable to use paracide.It is further possible to by different two or more polyhalo aromatic compound combinations and Copolymer is made, it preferably will be to di halo aromatic compound as main component.

About the usage amount of polyhalo aromatic compound, in terms of obtaining the PAS (A) suitable for the matter average molecular weight of processing Set out, may be exemplified every 1 mole of vulcanizing agent for 0.9~2.0 mole, preferably 0.95~1.5 mole, further preferably 1.005~1.2 moles of range.

As vulcanizing agent, alkali metal sulphide, alkali metal hydrosulfide and hydrogen sulfide can be enumerated.

As the concrete example of alkali metal sulphide, such as lithium sulfide, vulcanized sodium, potassium sulfide, rubidium sulfide, cesium sulfide can be enumerated With their mixtures of more than two kinds, wherein it is preferable to use vulcanized sodium.These alkali metal sulphides can be used as hydrate or aqueous Mixture is used in the form of anhydride.

As the concrete example of alkali metal hydrosulfide, such as sodium bisuflide, potassium hydrosulfide, hydrogen lithium sulfide, hydrogen sulphur can be enumerated Change rubidium, hydrogen cesium sulfide and their mixtures of more than two kinds, wherein it is preferable to use sodium bisuflides.These alkali metal hydrosulfides can To be used as hydrate or aqueous mixture, or in the form of anhydride.

In the manufacture of PAS (A), about the amount that vulcanizing agent is added, due to dehydrating operations etc. thus open in polymerization reaction In the case that a part of vulcanizing agent is lost before beginning, refer to the remaining after subtracting the loss part by actual additional amount Amount.

In addition, also can be together with vulcanizing agent and with alkali metal hydroxide and/or alkaline earth metal hydroxide.As alkali The concrete example of metal hydroxides, can enumerate for example sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and Their mixtures of more than two kinds are as preferred concrete example.As alkaline earth metal hydroxide, concrete example can enumerate such as hydrogen-oxygen Change calcium, strontium hydroxide, barium hydroxide etc., wherein it is preferable to use sodium hydroxides.

As vulcanizing agent, using alkali metal hydrosulfide, alkali metal hydroxide is particularly preferably used simultaneously Object, usage amount may be exemplified relative to 1 mole of alkali metal hydrosulfide be 0.95~1.20 mole, preferably 1.00~1.15 Mole, further preferably 1.005~1.100 moles of range.

Hereinafter, an example of the manufacturing method for PAS (A), by preceding process, polymerization reaction process, recovery process and rear place Science and engineering sequence successively specifically describes.

Preceding process is illustrated first.Vulcanizing agent uses usually in the form of hydrate, preferably in addition polyhalo virtue Before fragrant compounds of group, the mixture comprising organic polar solvent and vulcanizing agent is heated up, by the water of excess quantity remove to Outside system.In addition, the water of preferably addition insufficient section is supplemented in the case where exceedingly removing water by the operation.

In addition, also can be used as vulcanizing agent by alkali metal hydrosulfide and alkali metal hydroxide, in reaction system In the alkali metal sulphide modulated on the spot or using the slot different from polymerization tank.Modulation alkali metal sulphide optimum condition be Under non-active gas atmosphere, in room temperature~150 DEG C, the more preferably temperature range of room temperature~100 DEG C, in organic polar solvent Addition alkali metal hydrosulfide and alkali metal hydroxide are warming up to 150 DEG C or more, more preferably 180 under normal or reduced pressure ~260 DEG C, moisture is distilled off.Reagent and additive in polymerization can be added at this stage.In addition, in order to promote being distilled off for moisture, Toluene etc. can be added to be reacted.

The amount of moisture in polymerization system in polymerization reaction is to be added every 1 mole of vulcanizing agent preferably 0.5~10.0 mole. Here the amount of moisture in so-called polymerization system subtracts removing to the water outside polymerization system for the amount of moisture from being added to polymerization system It is measured obtained by component.In addition, the water being added can be any form of water, aqueous solution, the crystallization water etc..Amount of moisture it is preferred It is 0.75~2.5 mole that range, which is every 1 mole of vulcanizing agent, more preferably 1.0~1.25 moles of range.In order to which moisture is adjusted Extremely such range, also can before polymerization or moisture is added in polymerization midway.

In polymerization reaction process, make vulcanizing agent and polyhalo in the organic polar solvents such as n-methyl-2-pyrrolidone Aromatic compound is reacted within the scope of 200 DEG C or more 290 DEG C or less of temperature, to manufacture PAS (A).

When starting polymerization reaction process, preferably under non-active gas atmosphere, in room temperature~220 DEG C, preferably 100~ 220 DEG C of temperature range adds vulcanizing agent and polyhalo aromatic compound in organic polar solvent.It can add at this stage Add the reagent and additive in polymerization such as sodium acetate.Here, so-called reagent and additive in polymerization refers to the object adjust with the viscosity of resulting PAS (A) Matter.The addition sequence of these raw materials can be sequentially different, can also be simultaneously.

Such mixture is warming up to usual 200 DEG C~290 DEG C of range.Heating rate is not particularly limited, usually The speed of 0.01~5 DEG C/min of selection, more preferably 0.1~3 DEG C/min of range.

Finally, it is warming up to 250~290 DEG C of temperature, at the thermotonus 0.25~50 hour, preferably 0.5~20 is small When.

Stage before reaching final temperature, such as in 200 DEG C~245 DEG C reaction certain times, then heat to 250 ~290 DEG C of method is effective in the case where obtaining the higher degree of polymerization.At this point, as in 200 DEG C~245 DEG C of reaction Time usually selects in the range of 0.25 hour~20 hours, preferably selects in the range of 0.25~10 hour.

After polymerization, solid matter is recycled from the polymerization reactant comprising polymer, solvent etc..As recovery method, Such as flash method can be enumerated, that is, dodge polymerization reactant from the state of high temperature and pressure (usual 245 DEG C or more, 0.8MPa or more) It steams into normal pressure or the atmosphere of decompression, granular is made in polymer simultaneously with solvent recovery and the method that recycles；Quenching Method, that is, it is polymerization reactant is gradually cooling from the state of high temperature and pressure and make PAS in reaction system at analyzing, and At 70 DEG C or more, preferably 100 DEG C or more of state is filtered separation, so that particle is made in the solid comprising PAS ingredient Shape and the method etc. recycled.

The recovery method of PAS (A) is not limited to any one of quenching method, flash method, obtains preferably by quenching method PAS (A), because few as oligomer ingredient as representative using chloroform recovery ingredient, resulting fibre reinforced polyarylene sulfide Molding cycles it is excellent.As the oligomer extracted amount based on chloroform of the PAS obtained by quenching method, it may be exemplified 2 matter % is measured hereinafter, may be exemplified more preferably 1 mass % or less.

PAS (A) is to implement washing by hot water treatment, organic solvent after generating via above-mentioned polymerization, recovery process To use (postprocessing working procedures).The PAS (A) obtained via above-mentioned recovery process includes the alkali metal halogen as polymeric by-products Compound, alkali metal organic matter isoiony impurity, therefore carrying out washing is convention.Can enumerate as cleaning solution use such as water, The method that organic solvent is washed from simplicity and obtains PAS (A) aspect cheaply, may be exemplified and used water Washing is used as preferred method.Type as the water used is, it is preferable to use ion exchange water, distilled water.

Wash temperature when washing PAS (A) is preferably 50 DEG C or more 200 DEG C hereinafter, more preferably 150 DEG C or more 200 DEG C Hereinafter, further preferably 180 DEG C or more 200 DEG C or less.It is usually being provided using the operation of the processing of 100 DEG C or more of liquid The PAS (A) that specified amount is put into the liquid of amount, is heated in normal pressure or pressure vessel, is stirred to carry out.Washing can be into Repeatedly, wash temperature when each washing can be different for row, in order to obtain the few PAS of ionic impurity (A), can 150 DEG C with On temperature carry out at least 1 time, preferably carry out washing for 2 times or more, be carried out between each washing via by polymer and cleaning solution Isolated filter progress is preferred method.

When obtaining PAS (A), detergent additive can be used in the case where being washed, add as such washing Add agent, may be exemplified acid, alkali metal salt or alkali salt.Using acid, preferably in the water used in washing It adds organic acid or inorganic acid etc. and is made in acid aqueous solution, impregnate washed PAS, so that the water after heating washing The pH of solution becomes 2~8.As organic acid, inorganic acid, acetic acid, propionic acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid etc. may be exemplified, but It is not limited to this, preferably acetic acid, hydrochloric acid.In the present invention, the sour PAS (A) as detergent additive has been used to be referred to as acid End product.In the case where using alkali metal salt or alkali salt as detergent additive, it may be exemplified and used in washing Water in be added in the aqueous solution of alkali metal salt or alkali salt, the method for impregnating the PAS to be washed, such alkali gold The amount of category salt or alkali salt is preferably 0.01~5 mass %, further preferably 0.1~0.7 matter relative to PAS (A) Measure %.As alkali metal salt, alkali salt, calcium salt, sylvite, sodium salt, the magnesium salts of above-mentioned organic acid or inorganic acid may be exemplified Deng but not limited thereto.

Detergent additive can be used in the either phase of washing procedure, in order to using a small amount of additive efficiently into Row washing, is preferably washed the solid matter recycled using above-mentioned recovery process with water for several times, then added with washing It is impregnated with the PAS to be washed in the aqueous solution of additive, in the method that 150 DEG C or more are handled.PAS and washing when washing The preferred cleaning solution of the ratio of liquid is more, in general, preferably selecting the bath raio of PAS (A) 10~500g, further relative to 1 liter of cleaning solution Preferably 50~200g.

The PAS (A) being achieved in that is dried under normal pressure and/or under decompression.As such drying temperature, preferably 120~280 DEG C of range, more preferably 140~250 DEG C of range.It is inferior nonactive for nitrogen, helium, decompression to dry atmosphere Atmosphere, or the oxidizing atmospheres such as oxygen, air, any one of air and the mixed atmosphere of nitrogen, from melt viscosity Relationship set out, preferably inert atmosphere.Drying time is preferably 0.5~50 hour, and more preferably 1~30 hour, into one Step preferably 1~20 hour.

The poly- carbodiimide of < (B) >

As poly- carbodiimide (B), aliphatic poly carbodiimide and fragrant adoption carbodiimide may be exemplified.Poly- carbon two is sub- Amine (B) is not limited to any one of aliphatic poly carbodiimide, fragrant adoption carbodiimide, in order to make the reaction of carbodiimide Property it is high, the molding cycles of resulting fiber reinforcement polyarylene sulfide are excellent, preferably aliphatic poly carbodiimide.

So-called aliphatic poly carbodiimide, for general formula-N=C=N-R₃(in formula, R₃Indicate the ester ring types such as cyclohexylene The divalent of the aliphatic compounds such as the divalent organic group or methylene of compound, ethylidene, propylidene, methyl ethylidene is organic Group) shown in repetitive unit as main composition unit, containing the repetitive unit preferably 70 moles of % or more, more preferably The homopolymer or copolymer of 90 moles of % or more, further preferably 95 moles of % or more.

The synthetic method of aliphatic poly carbodiimide is not particularly limited, can be for example, by promoting organic multiple isocyanate Into isocyanate group carbodiimidization react catalyst (hereinafter also referred to " carbodiimidization catalyst ") in the presence of into Row reaction, thus synthctic fat adoption carbodiimide.

Organic multiple isocyanate used in synthesis as the aliphatic poly carbodiimide, preferably organic diisocyanate Ester.As such organic diisocyanate, can enumerate for example, ring butylidene -1,3- diisocyanate, ring pentylidene -1,3- Diisocyanate, cyclohexylene -1,3- diisocyanate, cyclohexylene -1,4- diisocyanate, methylcyclohexylidene -2 1-, 4- diisocyanate, 1- methylcyclohexylidene -2,6- diisocyanate, 1- isocyanates -3,3,5- trimethyl -5- isocyanates Hexahydrotoluene, hexamethylene -1,3- bis- (methyl isocyanates), hexamethylene -1,4- bis- (methyl isocyanates), dicyclohexyl first Alkane -2,4 '-diisocyanate, dicyclohexyl methyl hydride -4,4 '-diisocyanate, ethylidene diisocyanate, tetramethylene -1, 4- diisocyanate, hexa-methylene -1,6- diisocyanate, ten dimethylene -1,12- diisocyanate, two isocyanide of lysine Acid esters methyl ester etc., excess quantity and 2 functionality active hydrogen-contg compounds by the stoichiometries of these organic diisocyanates Reaction and the two terminal isocyanate prepolymers etc. that obtain.These organic diisocyanates can be used alone with a kind, or can also Two or more to be used in mixed way.

In addition, can be enumerated as the other organic multiple isocyanates being according to circumstances used together with organic diisocyanate For example, hexamethylene -1,3,5- triisocyanate, hexamethylene -1,3,5- tri- (methyl isocyanate), 3,5- dimethyl cyclohexane - 1,3,5- tri- (methyl isocyanate), 1,3,5- trimethyl-cyclohexane -1,3,5- three (methyl isocyanate), dicyclohexyl first Organic polyisocyanic acid more than 3 functions such as alkane -2,4,2 '-triisocyanate, dicyclohexyl methyl hydride -2,4,4 '-triisocyanate Ester, by more than the excess quantity of the stoichiometry of organic multiple isocyanates more than these 3 functions and 2 functions multi-functional containing living The reaction of property hydrogen compound and the terminal isocyanate prepolymer etc. obtained.

Above-mentioned other organic multiple isocyanates can be used alone with a kind, or two or more can also be used in mixed way, and be made Dosage is every 100 mass parts of organic diisocyanate, preferably 0~40 mass parts, more preferably 0~20 mass parts.

Further, in the synthesis of aliphatic poly carbodiimide, it can according to need addition organic single-isocyanate, thus The molecular weight of resulting aliphatic poly carbodiimide is suitably controlled.

As such organic single-isocyanate, it is different that such as methyl isocyanate, ethyl isocyanate, n-propyl can be enumerated The alkyl monoisocyanates classes, cyclohexyl such as cyanate, n-butyl isocyanate, laurel based isocyanate, stearic based isocyanate The naphthenic base monoisocyanates classes such as isocyanates, 4- isocyanatomethyl, 2,5- dimethyleyelohexane based isocyanate.

These organic single-isocyanates can be used alone with a kind, or two or more can also be used in mixed way, usage amount Desired molecular weight according to aliphatic poly carbodiimide etc. and change, every 100 mass parts of organic multiple isocyanate ingredient, it is excellent It is selected as 0~40 mass parts, more preferably 0~20 mass parts.

In addition, such as 1- phenyl -2- Phospholes -1- oxide, 1- benzene can be enumerated as carbodiimidization catalyst Base -3- methyl -2- Phospholes -1- oxide, 1- phenyl -2- Phospholes -1- sulfide, 1- phenyl -3- methyl -2- Phospholes -1- sulfide, 1- ethyl -2- Phospholes -1- oxide, 1- ethyl -3- methyl -2- Phospholes - 1- oxide, 1- ethyl -2- Phospholes -1- sulfide, 1- ethyl -3- methyl -2- Phospholes -1- sulfide, 1- Methyl -2- Phospholes -1- oxide, 1- methyl -3- methyl -2- Phospholes -1- oxide, 1- methyl -2- phospha Cyclopentene -1- sulfide, 1- methyl -3- methyl -2- Phospholes -1- sulfide, their 3- phospholene isomers The metal-carbonyls such as equal Phospholes compound, iron pentacarbonyl, di-iron enneacarbonyl, nickel carbonyl, tungsten carbonyl, chromium carbonyl are matched Acetylacetone,2,4-pentanedione complex, trimethyl phosphate, triethyl phosphate, the phosphoric acid of the metals such as position compound, beryllium, aluminium, zirconium, chromium, iron Phosphates such as three isopropyl esters, the tricresyl phosphate tert-butyl ester, triphenyl phosphate etc..

Above-mentioned carbodiimidization catalyst can be used alone with a kind, or two or more can also be used in mixed way.The catalysis The usage amount of agent is every 100 mass parts of organic multiple isocyanate ingredient, preferably 0.001~30 mass parts, more preferably 0.01 ~10 mass parts.

The temperature of the synthetic reaction of aliphatic poly carbodiimide is according to organic multiple isocyanate, organic single-isocyanate, carbon The type of diimine catalyst suitably select, and usually 20~200 DEG C.In the synthetic reaction of aliphatic poly carbodiimide When, organic multiple isocyanate and organic single-isocyanate ingredient whole amount can add before the reaction, or can be by part of it Or it all continuously or periodically adds in the reaction.

In addition it is also possible to by the compound that can be reacted with isocyanate group aliphatic poly carbodiimide synthetic reaction Appropriate reaction stage in initial stage to later period be added, the terminal isocyanate group of aliphatic poly carbodiimide is sealed It closes, adjusts the molecular weight of resulting aliphatic poly carbodiimide, it furthermore can also be in the synthetic reaction of aliphatic poly carbodiimide Later period addition, the molecular weight of resulting aliphatic poly carbodiimide is limited to specified value.As it is such can be with isocyanide Perester radical reaction compound, can enumerate the alcohols such as methanol, ethyl alcohol, isopropanol, cyclohexanol, dimethyl amine, diethylamide, The amines such as benzyl amine.

So-called fragrance adoption carbodiimide, for general formula-N=C=N-R₄(in formula, R₄Indicate benzene,toluene,xylene, connection The divalent organic group of the cyclic unsaturated compounds such as benzene, naphthalene, anthracene) shown in repetitive unit as main composition unit, contain The repetitive unit is preferably 70 moles of % or more, more preferably 90 moles of % or more, further preferably 95 moles of %'s or more Homopolymer or copolymer.

As fragrant adoption carbodiimide, ライ Application ケミー society's system " スタバ Network ゾー Le (registered trademark) " can be enumerated P, ライ Application ケミー society system " スタバクゾー Le (registered trademark) " P400 etc..

The matter average molecular weight of poly- carbodiimide (B) is preferably 500~40,000, more preferably 1,000~5,000.If The matter average molecular weight of poly- carbodiimide (B) is less than 500, then molding cycles of resulting fibre reinforced polyarylene sulfide sometimes It reduces.If the matter average molecular weight of poly- carbodiimide (B) is greater than 40,000, then reduced sometimes with the melting and mixing of PAS (A), The molding cycles of resulting fibre reinforced polyarylene sulfide reduce.In addition, the matter average molecular weight of poly- carbodiimide (B) can be with It is found out by analysis methods such as SEC (size exclusion chromatography).

< carbon fiber (D) >

As carbon fiber (D), polyacrylonitrile (PAN) based carbon fiber, pitch-based carbon fiber, artificial silk system carbon fiber can be used Dimension etc., can also making these fibers, two or more is mixed.

The tensile strength of carbon fiber (D) is preferably 2,000MPa or more, more preferably 3,000MPa or more, further preferably For 4,000MPa or more.In addition, the tensile modulus of elasticity of carbon fiber (D) is preferably 200GPa or more 700GPa or less.Further, The tensile elongation of carbon fiber (D) is preferably 0.5% or more, and more preferably 1.0% or more, further preferably 1.8% or more, Particularly preferably 2.0% or more.By using the carbon fiber (D) of high elongation rate, so as to be reached with high level through this hair The raising of mechanical characteristic as the tensile strength of the fibre reinforced polyarylene sulfide of bright acquisition, elongation, thus it is especially excellent Choosing.From the viewpoint of such tensile strength, tensile modulus of elasticity, tensile elongation balance, it is excellent as carbon fiber (D) Choosing uses PAN based carbon fiber.

The oxygen (O) for the fiber surface of carbon fiber (D) measured by X-ray photoelectron spectroscopy (XPS) and the original of carbon (C) The surface oxygen concentration ratio (O/C) of the ratio between subnumber is preferably 0.05~0.50, and more preferably 0.08~0.40, further preferably 0.10~0.30.Surface oxygen concentration ratio (O/C) is higher, then the amount of functional groups of carbon fiber surface is more, more can be improved with it is other On the other hand the cementability of ingredient if surface oxygen concentration ratio (O/C) is excessively high, worries the crystal structure of carbon fiber surface It destroys, therefore surface oxygen concentration ratio (O/C) can obtain the especially excellent fibre reinforced of mechanical characteristic in preferred range Polyarylene sulfide.

The surface oxygen concentration ratio (O/C) of carbon fiber (D) is found out according to the following steps by X-ray photoelectron spectroscopy. Firstly, the carbon fiber (D) for eliminating sizing agent etc. with solvent is carried out cutting and is unfolded to arrange in sample support table made of copper Afterwards, photoelectron abjection angle is set as 90 °, uses MgK as x-ray source_α1,2, 1 × 10 will be held in sample chamber^-8Support.Make The correction at the peak of electrification when for measurement, keeps the kinetic energy values (K.E.) of the main peak of C1S consistent with 969eV.C1S peak area is logical It crosses and draws the baseline of straight line in the range of 958~972eV as K.E. and find out.O1S peak area by as K.E. 714~ The range of 726eV is drawn the baseline of straight line and is found out.Here so-called surface oxygen concentration ratio (O/C), by above-mentioned O1S peak area with The ratio of C1S peak area, the intrinsic sensitivity correction value of use device and as atomicity than calculate.

As the method for control surface oxygen concentration ratio (O/C), it is not particularly limited, it can be using for example, at electrolytic oxidation The gimmicks such as reason, medical fluid oxidation processes and gaseous oxidation processing, wherein preferably electrolytic oxidation process.

In addition, the avarage fiber diameter of carbon fiber (D) is preferably more preferably 3~15 μm of model in the range of 1~20 μm In enclosing.By in the range that is set as such, in process (III-1), (III-2) or (III-3), mentioned component (C-1), (C- 2) or the Composite of (C-3) and carbon fiber (D) become easy, therefore preferably.

Carbon fiber (D) preferably in 1 molecule with 3 or more at least one kind of officials in carboxyl, hydroxyl and epoxy group The compound (hereinafter, being abbreviated as compound (E)) that can be rolled into a ball is surface-treated.Above-mentioned functional group can mix in 1 molecule There are two or more, the compound in 1 molecule with 3 or more a kind of functional groups can also be used in combination of two or more.It is being used only 1 In molecule less than the compound of 3 above-mentioned functional groups in the case where, sometimes with surface functional group, the mentioned component of carbon fiber (D) (C-1), the reaction site of (C-2) or (C-3) are insufficient, and the mechanical characteristic of resulting fibre reinforced polyarylene sulfide reduces.On The functional group other than functional group is stated, such as alkoxy silane lacks the reactivity with carbon fiber surface, therefore using in 1 molecule In the case where with each 1 silane coupling agent of alkoxy silane and epoxy group, cannot get sometimes it is of the invention as a purpose The excellent fibre reinforced polyarylene sulfide of mechanical characteristic.

As the concrete example of compound (E), polyfunctional epoxy resin, acrylic acid series polymeric compounds, polyalcohol etc. can be enumerated, it is special Not You Xuanwei with the surface functional group of carbon fiber (D), mentioned component (C-1), (C-2) or (C-3) it is with high reactivity multifunctional Epoxy resin.

As polyfunctional epoxy resin, aliphatic epoxy resin, the phenol novolak-type epoxy of 3 functions or more can be enumerated Resin etc..In addition, aliphatic epoxy resin more than so-called 3 function, refers to the fat in 1 molecule with 3 or more epoxy groups Race's epoxy resin.

As the concrete example of aliphatic epoxy resins more than 3 functions, can enumerate for example, glycerol triglycidyl ether, Two glycerol poly epihydric alcohol base ethers, polyglycereol poly epihydric alcohol base ether, D-sorbite poly epihydric alcohol base ether, arabite are poly- The aliphatic polyols such as glycidyl ether, trimethylolpropane tris glycidyl ether, pentaerythrite poly epihydric alcohol base ether Poly epihydric alcohol base ether etc..It largely include epoxy group with high reactivity from 1 molecule in these aliphatic epoxy resins, And high water solubility is easy to set out to the coating of carbon fiber (D), in the present invention it is preferable to use glycerol triglycidyl ether, Two glycerol poly epihydric alcohol base ethers, polyglycereol poly epihydric alcohol base ether.

So-called acrylic acid series polymeric compounds are the polymer of acrylic acid, methacrylic acid and maleic acid, are to contain 3 in 1 molecule The general name of the polymer of a above carboxyl.Specifically, can enumerate the copolymer of polyacrylic acid, acrylic acid and methacrylic acid, The copolymer or their mixture of more than two kinds of acrylic acid and maleic acid.Further, about acrylic acid series polymeric compounds, as long as The number of above-mentioned functional group is 3 or more in 1 molecule, so that it may which carboxyl is partly neutralized to (that is, becoming carboxylate) with alkali. As above-mentioned alkali, can enumerate for example, the alkali metal hydroxides such as sodium hydroxide, lithium hydroxide, potassium hydroxide, ammonium hydroxide etc.. As acrylic acid series polymeric compounds, it is preferable to use more wrapping carboxylic polyacrylic acid in 1 molecule.

As the concrete example of polyalcohol, polyvinyl alcohol, glycerol, two glycerol, polyglycereol, D-sorbite, Arab can be enumerated Sugar alcohol, trimethylolpropane, pentaerythrite etc..As polyalcohol, it is preferable to use more including the polyethylene of hydroxyl in 1 molecule Alcohol.

Compound (E) preferably by its matter average molecular weight divided by the above-mentioned functional group in 1 molecule number (carboxyl, hydroxyl and The sum of epoxy group) obtained by value be 40~150.By being set as such range, so as to so that compound (E) and carbon fiber (D) density of the reaction site of the carbodiimide of surface functional group, mentioned component (C-1), (C-2) or (C-3) more evenly, It can be further improved the mechanical characteristic of resulting fibre reinforced polyarylene sulfide.

Compound (E) is preferably in the interface of mentioned component (C-1), (C-2) or (C-3) and carbon fiber (D).Therefore, Compound (E) is coated on the surface of the monofilament of carbon fiber (D) and uses.By being assigned compound (E) in advance to carbon fiber (D), to can also be effectively modified on the surface of carbon fiber (D) even if being a small amount of adhesion amount.

The containing ratio of compound (E) is preferably 0.01~5 mass parts relative to 100 mass parts of carbon fiber (D), more preferably 0.1~2 mass parts.When the containing ratio of compound (E) is less than 0.01 mass parts, compound (E) cannot be fully coated sometimes The surface of carbon fiber (D) is not easy to show the improvement effect of the mechanical characteristic of resulting fibre reinforced polyarylene sulfide.In addition, If the containing ratio of compound (E) is more than 5 mass parts, compound (E) is formed by envelope on the surface of carbon fiber (D) Thickness is excessively increased, therefore sometimes reduces the mechanical characteristic of resulting fibre reinforced polyarylene sulfide.As compound (E) It is formed by the preferred range of the thickness of envelope on the surface of carbon fiber (D), may be exemplified 10~150nm.

In the present invention, it assigns as by compound (E) to the method for carbon fiber (D), can enumerate for example via making of roller Close the method that object (E) is impregnated in the substrate comprising carbon fiber (D)；Compound (E) is set to become misty and spray to comprising carbon fiber (D) method etc. of substrate.At this point, in order to make compound (E) for the monofilament of carbon fiber (D) adhesion amount more evenly, preferably Compound (E) is diluted with solvent, or temperature, spinline tension when control imparting etc..The solvent of diluted compounds (E) can Water, methanol, ethyl alcohol, dimethylformamide, dimethyl acetamide, acetone etc. are enumerated, from the viewpoint of operation is easy and takes precautions against natural calamities, Preferably water.Such solvent makes its steaming after assigning compound (E) to the substrate comprising carbon fiber (D), through heating It sends out and is removed.In addition, in the case where using compound that is insoluble or being insoluble in water as compound (E), preferred addition cream Agent or surfactant carry out water dispersion and use.As emulsifier or surfactant, anionic system emulsification can be used Agent, cationic system emulsifier, nonionic system emulsifier etc..Wherein it is not easy to damage using the small nonionic system emulsifier that interacts The effect of compound (E), therefore preferably.

The other additive > of <

In the present invention, in the range that does not impair the effects of the present invention, it can contain in fibre reinforced polyarylene sulfide The impact modifiers such as elastomer or rubber constituent, other filling materials, additive.As the example of additive, resistance can be enumerated Fire agent, conductivity-imparting agent, crystallization nucleating agent, ultraviolet absorbing agent, antioxidant, damping agent, antibacterial agent, insect-proof agent, deodorization Agent, coloring agent, heat stabilizer, release agent, antistatic agent, plasticizer, lubricant, colorant, pigment, dyestuff, foaming agent, Or infusion processed.

< has used the product > of fibre reinforced polyarylene sulfide

Present invention fibre reinforced polyarylene sulfide obtained as casting of electronic device be it is suitable, suitable for counting Calculate mechanical, electrical view, camera, audio player etc..

Present invention fibre reinforced polyarylene sulfide obtained is suitable for electrical and electronic parts purposes, suitable for connection Device, LED light, socket, optical take-up apparatus, terminal board, printed base plate, loudspeaker, miniature motor, magnetic head, power module, power generation Mechanical, electrical motivation, transformer, current transformer, voltage adjuster, rectifier, inverter etc..

Present invention fibre reinforced polyarylene sulfide obtained is suitable for automotive part, vehicle associated components etc., fits It shares in harness pieces, instrument board, armrest box, column, roof rail, mud guard, buffer, door skin, roof panels, hair Motivation cover plate part, luggage-boot lid, peephole frame, spoiler, hood air channel, car wheel cover, wheel cover, decoration, air inlet discrimination Pipe, petrolift, engine cool water swivel, window cleaning device nozzle, wiper, battery circumferential component, Wiring connector, lamp Shell, lamp reflector, lamp holder etc..

Present invention fibre reinforced polyarylene sulfide obtained as building materials be it is suitable, suitable for civil construction object Wall, roof, ceiling material associated components, window material associated components, heat insulating material associated components, flooring board associated components, exempt from shake resistance Buddhist nun's component associated components, life line associated components etc..

Present invention fibre reinforced polyarylene sulfide obtained as sports goods be it is suitable, suitable for golf The sport racket such as the golf such as club, golf of bat related supplies, tennis racket, racket related supplies, American olive The sport such as mask, the helmet, chest protector, elbow support, the knee-pad of olive ball, baseball, softball etc. bodily protection articles, fishing rod, fishing line, bait Winter sports related supplies such as equal fishing tackle related supplies, skiing, skis etc..

Embodiment

Embodiment described below, further specifically describes the present invention.

Firstly, evaluation method used in the present invention is described below.

(1) leak test

Resulting fibre reinforced polyarylene sulfide is processed into the shape of test film (200mm × 200mm, thickness 1mm). The test film is clamped between the 2 pieces of stainless steel plates (300mm × 300mm, thickness 10mm, mirror finish) for being preheated to 300 DEG C, Investment is press-formed to pressure forming machine.Extrusion forming temperature is set as 300 DEG C, and extrusion forming pressure is set as 0.5MPa, pressurizes Molding time is set as 3 minutes.Next test film is taken out in the state of being clipped by 2 pieces of stainless steel plates from pressure forming machine, Test film and stainless steel plate are separated into after being cooled to room temperature.Above operation is set as 1 and penetrates (shot), only recycles stainless steel Plate carries out penetrating molding more, leakage when evaluation processing and forming recycles.Evaluation is penetrated the 10th injects row with the 30th, by stainless steel The surface of plate it is the presence or absence of fuzzy as benchmark is judged, evaluated using 3 grade below, will be excellent or well be set as closing Lattice.

Excellent: even if the 30th penetrates, the surface of stainless steel plate is also without fuzzy.

Good: at the time of the 10th penetrates, the surface of stainless steel plate is not obscured, but at the time of the 30th penetrates, stainless steel plate Surface observe it is fuzzy.

Difference: at the time of the 10th penetrates, the surface of stainless steel plate is observed fuzzy.

(2) tension test of fibre reinforced polyarylene sulfide

According to ASTM D638, used " イ Application ストロ Application (registered trademark) " using Type-I test film as testing machine Universal testing machine (イ Application ストロ Application society system).So-called tensile elongation refers to that the breaking point measured using strain gauge is answered Become.

(3) heat resisting temperature of poly- carbodiimide reactant (B-2)

As testing machine, thermogravimetry device (パーキ Application エルマー society TGA7 is used).In addition, sample uses 2mm shot-like particle below.Using sample 10mg, 400 are heated to 20 DEG C/min from 30 DEG C of heating rate in air atmosphere DEG C, measure the mass change of sample.In this operation, the quality of sample is reduced to temperature when 5 mass % from 30 DEG C of moment It is set as heat resisting temperature.

(4) mold fouling is evaluated

In process (V), the surface of molding die when being injection moulded by observation, thus when evaluating processing and forming circulation Mold fouling.Make by process (III-1), (III-2) or (III-3) complex obtained or have passed through answering for process (IV) Zoarium is molten condition in the barrel of injection (mo(u)lding) machine, and then the complex of the molten condition is injected in molding die, Cooling, solidification, so that the injection-molded article of defined shape be made and take out, the above operation, which is set as 1, is penetrated, and recycles shaping mould Tool carries out the mold foulings penetrated molding, evaluate when processing and forming circulation more.Evaluation penetrates the 10th and injects row with the 30th, will be at The surface of pattern tool it is the presence or absence of fuzzy as benchmark is judged, evaluated using 3 grade below, will be excellent or be well set as It is qualified.

Excellent: even if penetrating the 30th, the surface of molding die is also without fuzzy.

Good: at the time of the 10th penetrates, the surface of molding die is not obscured, but at the time of the 30th penetrates, molding die Surface observe it is fuzzy.

Difference: at the time of the 10th penetrates, the surface of molding die is observed fuzzy.

PAS used in embodiment and comparative example (A) is as follows.

(PPS-1) 285 DEG C of fusing point, 90 DEG C of glass transition temperature, matter average molecular weight 30,000, sour end product, chloroform mentions The polyphenylene sulfide of 0.5 mass % of taken amount

Poly- carbodiimide (B) used in reference example, embodiment and comparative example is as follows.

(CDI-1) aliphatic poly carbodiimide " " カ Le ボジライト (registered trademark) " HMV-8CA (Nisshinbo ケミカ Le society system) " (carbodiimide equivalent 278, matter average molecular weight 3,000,70 DEG C of softening point)

Single carbon diimine (B ') used in comparative example is as follows.

(CDI-2) N, N ' (carbodiimide equivalent 206, matter is equal for-dicyclohexylcarbodiimide (Wako Pure Chemical Industries, Ltd.'s system) Molecular weight 206)

Carbon fiber used in reference example, embodiment and comparative example (D) is as follows.

(CF-1) by using using polyacrylonitrile as the copolymer of principal component, spinning, firing processing and Surface Oxygen are carried out Change processing, to obtain total number of monofilament 12,000 continuous carbon fibre tow.The characteristic of the carbon fiber is as follows.

Tensile strength: 4,900MPa

Tensile modulus of elasticity: 240GPa

Tensile elongation: 2%

Specific gravity: 1.8

Filament diameter: 7 μm

Surface oxygen concentration ratio [O/C]: 0.12

Compound used in reference example, embodiment and comparative example (E) is as follows.

(E-1) glycerol triglycidyl ether (Wako Pure Chemical Industries, Ltd.'s system)

Matter average molecular weight: 260

The epoxy radix of every 1 molecule: 3

By matter average molecular weight divided by the carboxyl of every 1 molecule, hydroxyl, epoxy group, hydroxyl sum obtained by be worth: 87

(E-2) polyacrylic acid (SIGMA-ALDRICH society system)

Matter average molecular weight: 2,000

The carboxyl number of every 1 molecule: 27

By matter average molecular weight divided by the carboxyl of every 1 molecule, hydroxyl, epoxy group, hydroxyl sum obtained by be worth: 74

(E-3) polyvinyl alcohol (Wako Pure Chemical Industries, Ltd.'s system)

Matter average molecular weight: 22,000

The hydroxyl value of every 1 molecule: 500

By matter average molecular weight divided by the carboxyl of every 1 molecule, hydroxyl, epoxy group, hydroxyl sum obtained by be worth: 44

(reference example 1)

CF-1 is cut into length 6mm with boxlike cutting machine (cartridge cutter), obtains chopped carbon fiber.System Make to include water and surfactant (Na カライテ Network ス society system, Port リオキシエチレ Application ラウリルエーテ Le (commodity Name)) 0.1 mass % of concentration dispersion liquid, add chopped carbon fiber in the dispersion liquid, be stirred, to obtain carbon The carbon fiber dispersion liquid of 0.05 mass % of fibre concentration.The carbon fiber dispersion liquid is transferred to the sieve that bottom has diameter 500mm The cylindrical shape container of pore structure, is filtered, and is next made residue heat drying 30 minutes in 200 DEG C of drying oven, is obtained Obtained the carbon fiber base material (CFM-1) of non-woven fabrics.The metsuke of resulting CFM-1 is 50g/m²。

(reference example 2)

Use E-1 as ingredient (E), in the water-based dispersion mother liquor comprising 2 mass % of ingredient (E), impregnates by referring to The CFM-1 that example 1 makes, is then dried at 230 DEG C, to obtain the carbon comprising being surface-treated with ingredient (E) The substrate (CFM-2) of fiber (D).The adhesion amount of ingredient (E) after drying is 1 mass relative to 100 mass parts of carbon fiber (D) Part.

(reference example 3)

Use E-2 as ingredient (E), in the water-based dispersion mother liquor comprising 2 mass % of ingredient (E), impregnates by referring to The CFM-1 that example 1 makes, is then dried at 230 DEG C, to obtain the carbon comprising being surface-treated with ingredient (E) The substrate (CFM-3) of fiber (D).The adhesion amount of ingredient (E) after drying is 1 mass relative to 100 mass parts of carbon fiber (D) Part.

(reference example 4)

Use E-3 as ingredient (E), in the water-based dispersion mother liquor comprising 2 mass % of ingredient (E), impregnates by referring to The CFM-1 that example 1 makes, is then dried at 230 DEG C, to obtain the carbon comprising being surface-treated with ingredient (E) The substrate (CFM-4) of fiber (D).The adhesion amount of ingredient (E) after drying is 1 mass relative to 100 mass parts of carbon fiber (D) Part.

(embodiment 1)

Using ingredient shown in table 1, condition, be related to by the one embodiment of the present invention using following step 1 manufacturing method manufactures fibre reinforced polyarylene sulfide, is evaluated.

Process (I-1): obtaining makes PAS (A) and mixture that poly- carbodiimide (B) dry type has blended, put into Labo Plastomill device (Toyo Seiki makes institute's 4C150 type, R-60 type mixing machine), carries out melting mixing, to obtain Melting mixing object.

Process (II-1): resulting melting mixing object is directly transferred to pressure forming machine in the molten state, is obtained Film comprising poly- carbodiimide modified polyarylene sulfide (C-1).

Process (III-1): by the carbon fiber base material (CFM-2) of resulting film and non-woven fabrics alternately lamination, investment To pressure forming machine, to produce fibre reinforced polyarylene sulfide.

Test film is cut out from resulting fibre reinforced polyarylene sulfide, for each test.Evaluation result is recorded in In table 1.

(comparative example 1)

The melting mixing time in process (I-1) is replaced with 3,600 seconds, the press temperature in process (II-1) is replaced It is 50 DEG C, will further replaces with the pressing time 300 seconds, in addition to this, using method similarly to Example 1, it is desirable to make Test film, as a result the Composite of the poly- carbodiimide modified polyarylene sulfide (C-1) in process (III-1) and carbon fiber (D) are tired Difficulty cannot obtain fibre reinforced polyarylene sulfide.Evaluation result is recorded in table 1.

(embodiment 2)

Pressing time in process (II-1) is replaced with 1,800 seconds, in addition to this, using side similarly to Example 1 Method makes test film, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 3)

Pressing time in process (II-1) is replaced with 900 seconds, in addition to this, using method similarly to Example 1, Test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 4)

Press temperature in process (II-1) is replaced with 200 DEG C, in addition to this, using method similarly to Example 1, Test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 5)

Press temperature in process (II-1) is replaced with 150 DEG C, in addition to this, using method similarly to Example 1, Test film is made, for each evaluation.Evaluation result is recorded in table 1.

(comparative example 2)

Press temperature in process (II-1) is replaced with 50 DEG C, in addition to this, using method similarly to Example 1, Test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 6)

The melting mixing time in process (I-1) is replaced with 45 seconds, in addition to this, using side similarly to Example 1 Method makes test film, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 7)

It is 1 mass parts that the amount of poly- carbodiimide (B), which is replaced with relative to 100 mass parts of PAS (A), in addition to this, is used Method similarly to Example 1 makes test film, for each evaluation.Evaluation result is recorded in table 1.

(comparative example 3)

Without poly- carbodiimide (B), in addition to this, using method similarly to Example 1, test film is made, for each Evaluation.Evaluation result is recorded in table 1.

(comparative example 4)

It is that 20 mass parts are adopted in addition to this that the amount of poly- carbodiimide (B), which is replaced with relative to 100 mass parts of PAS (A), With method similarly to Example 1, test film is made, for each evaluation.Evaluation result is recorded in table 1.

(comparative example 5)

Instead of poly- carbodiimide (B), used as the CDI-2 of single carbon diimine (B '), in addition to this, use and embodiment 1 same method makes test film, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 8)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of nonwoven The content of the carbon fiber base material (CFM-2) of cloth shape is so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 25 mass Part, in addition to this, using method similarly to Example 1, test film is made, for each evaluation.Evaluation result is recorded in table 1 In.

(embodiment 9)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of nonwoven The content of the carbon fiber base material (CFM-2) of cloth shape is so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 100 matter Part is measured, in addition to this, using method similarly to Example 1, test film is made, for each evaluation.Evaluation result is recorded in In table 1.

(embodiment 10)

Due to making ingredient (E) to be E-2, adopted in addition to this using the carbon fiber base material (CFM-3) of non-woven fabrics With method similarly to Example 1, test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 11)

Due to making ingredient (E) to be E-3, adopted in addition to this using the carbon fiber base material (CFM-4) of non-woven fabrics With method similarly to Example 1, test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 12)

By without in a manner of ingredient (E), using the carbon fiber base material (CFM-1) of non-woven fabrics, in addition to this, using with The same method of embodiment 1 makes test film, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 13)

In process (I-1), by the mixing machine part of Labo Plastomill device with having vacuum meter and vacuum pump Vacuum tank it is coating, be adjusted such that the degree of decompression in the vacuum tank in melting mixing becomes -0.1MPa, except this with Outside, using method similarly to Example 3, test film is made, for each evaluation.Evaluation result is recorded in table 1.

(embodiment 14)

To put into again by the fibre reinforced polyarylene sulfide that process (III-1) is obtained as process (IV) extremely pressurize at Type machine is heated under conditions of 250 DEG C of press temperature, pressing pressure 0.5MPa, the pressing time 3600 seconds, in addition to this, Using method similarly to Example 3, test film is made, for each evaluation.Evaluation result is recorded in table 1.

Table 1

Content below is specified by the embodiment and comparative example of table 1.

In embodiment 1, due to meeting the whole important documents of process (I-1)~(III-1), mechanical characteristic and molding are had both The productivity of cyclicity, fibre reinforced polyarylene sulfide is also excellent.

In comparative example 1, due to making the melting mixing time in process (I-1) for a long time, even if in process (II-1) It is heated to be low temperature and short time, the poly- carbodiimide modified polyarylene sulfide (C-1) in process (III-1) and carbon fiber (D) Composite it is also difficult.

By the comparison of Examples 1 to 3 it is found that more than the glass transition temperature of the PAS (A) in process (II-1) and The time that fusing point temperature below is heated is longer, then the leakage ingredient of resulting fibre reinforced polyarylene sulfide more subtracts Few, molding cycles more improve.

By embodiment 1,4,5 it is found that by turning in process (II-1) in the vitrifying of PAS (A) compared with comparative example 2 More than temperature and fusing point temperature below is heated, thus the leakage ingredient of resulting fibre reinforced polyarylene sulfide It reduces, molding cycles improve.

By embodiment 1 it is found that resulting fibre reinforced is poly- in process (I-1) when t1 < t2 compared with embodiment 6 The leakage ingredient of arylene sulfide is reduced, and molding cycles improve.

By embodiment 1,7 it is found that by making the amount of poly- carbodiimide (B) relative to PAS (A) compared with comparative example 3,4 100 mass parts are 0.1~10 mass parts, can obtain the fibre reinforced polyarylene sulfide for having both mechanical characteristic and molding cycles Ether.

By embodiment 1 it is found that by using having the above carbodiimide of at least two in 1 molecule compared with comparative example 5 Poly- carbodiimide (B), the fibre reinforced polyarylene sulfide for having both mechanical characteristic and molding cycles can be obtained.

By embodiment 1,8,9 it is found that even if changing the amount of carbon fiber (D), it is also possible to obtain have both mechanical characteristic and molding Circulative fibre reinforced polyarylene sulfide.

Mechanical characteristic can be obtained it is found that by using ingredient (E) compared with embodiment 12 by embodiment 1,10,11 Superior fibre reinforced polyarylene sulfide.

By embodiment 13 it is found that mixed by the melting for being performed under reduced pressure process (I-1) compared with embodiment 3 The leakage ingredient of refining, resulting fibre reinforced polyarylene sulfide is reduced, and molding cycles improve.

By embodiment 14 it is found that will be obtained by process (III-1) by as process (IV) compared with embodiment 3 Fibre reinforced polyarylene sulfide is more than the glass transition temperature of PAS (A) and fusing point temperature below is heated, from And the leakage ingredient of resulting fibre reinforced polyarylene sulfide is reduced, molding cycles improve.

(reference example 5)

By as process (I-2), with heating temperature documented by table 2 and heating time, by poly- carbon in hot-air oven Diimine (B) is heated, to obtain CDI-3 as poly- carbodiimide reactant (B-2).Pass through thermogravimetry device The heat resisting temperature of resulting CDI-3 is measured, evaluation result is recorded in table 2.

(reference example 6)

Make 200 DEG C of heating temperature, will replace with heating time 2 hours, in addition to this, using same as reference example 5 Method heats poly- carbodiimide (B), to obtain CDI-4 as poly- carbodiimide reactant (B-2).Pass through heat Gravimetric analysis device measures the heat resisting temperature of resulting CDI-4, and evaluation result is recorded in table 2.

(reference example 7)

Make 300 DEG C of heating temperature, will replace with heating time 0.5 hour, in addition to this, using same as reference example 5 Method, poly- carbodiimide (B) is heated, to obtain CDI-5 as poly- carbodiimide reactant (B-2).Pass through Thermogravimetry device measures the heat resisting temperature of resulting CDI-5, and evaluation result is recorded in table 2.

(reference example 8)

Vacuum drying oven and vacuum pump, the degree of decompression being adjusted such that in above-mentioned vacuum drying oven are used instead of hot-air oven As -0.1MPa, in addition to this, using method same as reference example 5, poly- carbodiimide (B) is heated, to obtain CDI-6 is as poly- carbodiimide reactant (B-2).The heat-resisting temperature of resulting CDI-6 is measured by thermogravimetry device Degree, evaluation result is recorded in table 2.

(reference example 9)

Make 100 DEG C of heating temperature, will replace with heating time 1 hour, in addition to this, using same as reference example 5 Method heats poly- carbodiimide (B), to obtain CDI-7 as poly- carbodiimide reactant (B-2).Pass through heat Gravimetric analysis device measures the heat resisting temperature of resulting CDI-7, and evaluation result is recorded in table 2.

(reference example 10)

As documented by table 2, instead of the CDI-1 as poly- carbodiimide (B), used as single carbon diimine (B ') CDI-2 using method same as reference example 5, attempted heating operation in addition to this, as a result CDI-2 can volatilize, and obtain not To the reactant formed by single carbon diimine.

(reference example 11)

The heat resisting temperature that the CDI-1 as poly- carbodiimide (B) is measured by thermogravimetry device, by evaluation result It is recorded in table 2.

Table 2

(embodiment 15)

Using ingredient shown in table 3, condition, be related to by the one embodiment of the present invention using following step 2 manufacturing methods manufacture fibre reinforced polyarylene sulfide, are evaluated.

Process (II-2): by PAS (A) and poly- carbodiimide reactant (B-2) to biaxial extruder (JSW society TEX-30 α, (spiro rod length)/(screw diameter)=31.5) main feed and carry out melting mixing.Melting mixing is carried out at 300 DEG C of barrel temperature, From by each ingredient main feed up to be discharged required for the time (melting mixing time) be 150 seconds.Melting mixing object is from being installed on The T-shaped mould of biaxial extruder front end is discharged, and is cooled down using chill roll, to obtain comprising the poly- virtue of poly- carbodiimide modified Support the film of thioether (C-2).

Process (III-2): being cut into defined size for the film of acquisition, the carbon fiber base material (CFM- with non-woven fabrics 2) alternately lamination is put into pressure forming machine, to produce fibre reinforced polyarylene sulfide.

Test film is cut out from resulting fibre reinforced polyarylene sulfide, for each test.Evaluation result is recorded in table 3.

(embodiment 16)

Use CDI-4 as poly- carbodiimide reactant (B-2), in addition to this, using method similarly to Example 15, Test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 17)

Use CDI-5 as poly- carbodiimide reactant (B-2), in addition to this, using method similarly to Example 15, Test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 18)

Use CDI-6 as poly- carbodiimide reactant (B-2), in addition to this, using method similarly to Example 15, Test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 19)

Use CDI-7 as poly- carbodiimide reactant (B-2), in addition to this, using method similarly to Example 15, Test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 20)

To put into again by the fibre reinforced polyarylene sulfide that process (III-2) is obtained as process (IV) extremely pressurize at Type machine is heated under conditions of 250 DEG C of press temperature, pressing pressure 0.5MPa, the pressing time 3600 seconds, in addition to this, Using method similarly to Example 19, test film is made, for each evaluation.Evaluation result is recorded in table 3.

(comparative example 6)

Without poly- carbodiimide reactant (B-2), in addition to this, using method similarly to Example 15, production test Piece, for each evaluation.Evaluation result is recorded in table 3.

(comparative example 7)

Instead of poly- carbodiimide reactant (B-2), used as the CDI-2 of single carbon diimine (B '), in addition to this, use Method similarly to Example 15 makes test film, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 21)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of non-woven fabrics The content of the carbon fiber base material (CFM-2) of shape so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 25 mass parts, In addition to this, using method similarly to Example 15, test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 22)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of non-woven fabrics The content of the carbon fiber base material (CFM-2) of shape so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 100 mass parts, In addition to this, using method similarly to Example 15, test film is made, for each evaluation.Evaluation result is recorded in table 3.

(embodiment 23)

Without ingredient (E), using the carbon fiber base material (CFM-1) of non-woven fabrics, in addition to this, using with embodiment 15 Same method makes test film, for each evaluation.Evaluation result is recorded in table 3.

Table 3

The following contents is specified by the reference example of table 2 and the embodiment and comparative example of table 3.

By reference to example 5~8 it is found that poly- carbodiimide (B) meets the important document of process (I-2) compared with reference example 11, To which heat resistance improves.

By reference to example 5~8 it is found that using single carbon two sub- in replacement poly- carbodiimide (B) compared with reference example 10 In the case where amine (B '), heat resistance is insufficient.

In embodiment 15, due to meeting the whole important documents of process (I-2)~(III-2), have both mechanical characteristic and at The productivity of type cyclicity, fibre reinforced polyarylene sulfide is also excellent.

By the comparison of embodiment 15~18 it is found that by the poly- carbodiimide (B) in process (II-2) in the soft of the ingredient The temperature when temperature of change or more is heated is lower in such condition, then resulting fibre reinforced polyarylene sulfide Mechanical characteristic more can be improved.

By embodiment 19 it is found that will be obtained by process (III-2) by as process (IV) compared with embodiment 20 Fibre reinforced polyarylene sulfide is more than the glass transition temperature of PAS (A) and fusing point temperature below is heated, from And the leakage ingredient of resulting fibre reinforced polyarylene sulfide is reduced, molding cycles improve.

By embodiment 15 it is found that by using poly- carbodiimide reactant (B-2) compared with comparative example 6,7, so as to To obtain the fibre reinforced polyarylene sulfide for having both mechanical characteristic and molding cycles.

By embodiment 15,21,22 it is found that even if change carbon fiber (D) amount, it is also possible to obtain have both mechanical characteristic and at The circulative fibre reinforced polyarylene sulfide of type.

By embodiment 15 it is found that it is more excellent mechanical characteristic can be obtained by using ingredient (E) compared with embodiment 23 Fibre reinforced polyarylene sulfide.

(embodiment 24)

Using ingredient shown in table 4, condition, be related to by the one embodiment of the present invention using following step 3 manufacturing methods manufacture fibre reinforced polyarylene sulfide, are evaluated.

Process (I-3): the mixture for making PAS (A) and poly- carbodiimide (B) to have carried out dry type blending is obtained.

Process (II-3): by resulting mixture to biaxial extruder (JSW society TEX-30 α, (spiro rod length)/(screw rod is straight Diameter)=31.5) main feed and carry out melting mixing.Melting mixing is carried out at 350 DEG C of barrel temperature, from each ingredient main feed is straight The time (melting mixing time) to required for being discharged is 300 seconds.Melting mixing object is from the T-type for being installed on biaxial extruder front end Mould discharge, is cooled down using chill roll, to obtain the film comprising poly- carbodiimide modified polyarylene sulfide (C-3).

Process (III-3): being cut into defined size for resulting film, the carbon fiber base material (CFM- with non-woven fabrics 2) alternately lamination is put into pressure forming machine, to produce fibre reinforced polyarylene sulfide.

Test film is cut out by resulting fibre reinforced polyarylene sulfide, for each test.Evaluation result is recorded in table 4 In.

(embodiment 25)

The barrel temperature of biaxial extruder in process (II-3) is replaced with 330 DEG C, in addition to this, use and embodiment 24 same methods make test film, for each evaluation.Evaluation result is recorded in table 4.

(embodiment 26)

To put into again by the fibre reinforced polyarylene sulfide that process (III-3) is obtained as process (IV) extremely pressurize at Type machine is heated under conditions of 250 DEG C of press temperature, pressing pressure 0.5MPa, the pressing time 3600 seconds, in addition to this, Using method similarly to Example 25, test film is made, for each evaluation.Evaluation result is recorded in table 4.

(comparative example 8)

The barrel temperature of biaxial extruder in process (II-3) is replaced with 300 DEG C, it further will be in process (III-3) Press temperature replace with 350 DEG C, in addition to this, using method similarly to Example 24, test film is made, for respectively commenting Valence.Evaluation result is recorded in table 4.

(comparative example 9)

Press temperature in process (III-3) is replaced with 420 DEG C, in addition to this, using side similarly to Example 24 Method, it is desirable to make test film, as a result the poly- carbodiimide modified polyarylene sulfide (C-3) in process (III-3) and carbon fiber (D) Composite it is difficult, fibre reinforced polyarylene sulfide cannot be obtained.Evaluation result is recorded in table 4.

(comparative example 10)

Without poly- carbodiimide (B), in addition to this, using method similarly to Example 24, test film is made, for each Evaluation.Evaluation result is recorded in table 4.

(comparative example 11)

It is that 20 mass parts are adopted in addition to this that the amount of poly- carbodiimide (B), which is replaced with relative to 100 mass parts of PAS (A), With method similarly to Example 24, test film is made, for each evaluation.Evaluation result is recorded in table 4.

(comparative example 12)

Instead of poly- carbodiimide (B), used as the CDI-2 of single carbon diimine (B '), in addition to this, use and embodiment 24 same methods make test film, for each evaluation.Evaluation result is recorded in table 4.

(embodiment 27)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of nonwoven The content of the carbon fiber base material (CFM-2) of cloth shape is so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 25 mass Part, in addition to this, using method similarly to Example 24, test film is made, for each evaluation.Evaluation result is recorded in table In 4.

(embodiment 28)

In the state of making the adhesion amount of ingredient (E) relative to carbon fiber (D) 100 1 mass parts of mass parts, instead of nonwoven The content of the carbon fiber base material (CFM-2) of cloth shape is so that the amount of carbon fiber (D) relative to 100 mass parts of PAS (A) is 100 matter Part is measured, in addition to this, using method similarly to Example 24, test film is made, for each evaluation.Evaluation result is recorded in In table 4.

(embodiment 29)

Without ingredient (E), using the carbon fiber base material (CFM-1) of non-woven fabrics, in addition to this, using with embodiment 24 Same method makes test film, for each evaluation.Evaluation result is recorded in table 4.

Table 4

The following contents is specified by the embodiment and comparative example of table 4.

In embodiment 24,25, due to meeting the whole important documents of process (I-3)~(III-3), have both mechanical characteristic and The productivity of molding cycles, fibre reinforced polyarylene sulfide is also excellent.

By embodiment 25 it is found that will be obtained by process (III-3) by as process (IV) compared with embodiment 26 Fibre reinforced polyarylene sulfide is more than the glass transition temperature of PAS (A) and fusing point temperature below is heated, from And the leakage ingredient of resulting fibre reinforced polyarylene sulfide is reduced, molding cycles improve.

By embodiment 24,25 it is found that in comparative example 8 compared with comparative example 8, due to being unsatisfactory for process (III-3) Important document, therefore the molding cycles of resulting fibre reinforced polyarylene sulfide are poor.

In comparative example 9, since the high temperature by process (III-3) at 400 DEG C or more carries out, poly- carbodiimide modified is poly- The Composite of arylene sulfide (C-3) and carbon fiber (D) are difficult.

By embodiment 24 it is found that by making the amount of poly- carbodiimide (B) relative to PAS (A) compared with comparative example 10,11 100 mass parts are 0.1~10 mass parts, it is hereby achieved that the poly- virtue of the fibre reinforced for having both mechanical characteristic and molding cycles Support thioether.

By embodiment 24 it is found that by using having the above carbodiimide of at least two in 1 molecule compared with comparative example 12 The poly- carbodiimide (B) of base, it is hereby achieved that having both the fibre reinforced polyarylene sulfide of mechanical characteristic and molding cycles.

By embodiment 24,27,28 it is found that even if change carbon fiber (D) amount, it is also possible to obtain have both mechanical characteristic and at The circulative fibre reinforced polyarylene sulfide of type.

By embodiment 24 it is found that it is more excellent mechanical characteristic can be obtained by using ingredient (E) compared with embodiment 29 Fibre reinforced polyarylene sulfide.

(embodiment 30)

Using ingredient shown in table 5, condition, be related to by the one embodiment of the present invention using following step 1 manufacturing method manufactures fibre reinforced polyarylene sulfide, is evaluated.

As process (V), the complex obtained by the process of embodiment 1 (III-1) is cut off, average grain diameter 5mm is made Particle above-mentioned particle is used to be injection moulded, to make test film using injection (mo(u)lding) machine (JSW society J150EII-P). Maximum pressure when being injection moulded is set as being injection moulded by injection moulding in 300 DEG C of barrel temperature, 150 DEG C of mold temperature progress Pressure.Evaluation result is recorded in table 5.

(embodiment 31)

The complex obtained using the process (III-1) by embodiment 3, in addition to this, using similarly to Example 30 Method makes test film, for each evaluation.Evaluation result is recorded in table 5.

(embodiment 32)

Injection molding barrel temperature in process (V) is replaced with 290 DEG C, in addition to this, using same with embodiment 31 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 5.

(embodiment 33)

Injection molding barrel temperature in process (V) is replaced with 350 DEG C, in addition to this, using same with embodiment 31 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 5.

(embodiment 34)

The complex obtained using the process (IV) by embodiment 14, in addition to this, using side similarly to Example 30 Method makes test film, for each evaluation.Evaluation result is recorded in table 5.

Table 5

In embodiment 30, due to meeting process (I-1)~(III-1) and process (V), mechanical characteristic and molding are had both The productivity of cyclicity, fibre reinforced polyarylene sulfide is also excellent.

In embodiment 34, due to meeting process (I-1)~(III-1), process (IV) and process (V), mechanics is had both The productivity of characteristic and molding cycles, fibre reinforced polyarylene sulfide is also excellent.

By the comparison of embodiment 31,32,33 it is found that by process (V), by processing and forming temperature when being injection moulded The low temperature of temperature when than obtaining complex in process (III-1) carries out, thus resulting fibre reinforced polyarylene sulfide The leakage ingredient of ether is reduced, and molding cycles improve.

(embodiment 35)

Using ingredient shown in table 6, condition, be related to by the one embodiment of the present invention using following step 2 manufacturing methods manufacture fibre reinforced polyarylene sulfide, are evaluated.

As process (V), the complex obtained by the process of embodiment 15 (III-2) is cut off, average grain diameter 5mm is made Particle.Using injection (mo(u)lding) machine (JSW society J150EII-P), above-mentioned particle is used to be injection moulded, to produce test Piece.Maximum pressure when being injection moulded is set as being injected by injection moulding in 300 DEG C of barrel temperature, 150 DEG C of mold temperature progress Type pressure.Evaluation result is recorded in table 6.

(embodiment 36)

The complex obtained using the process (III-2) by embodiment 19, in addition to this, using same as embodiment 35 Method makes test film, for each evaluation.Evaluation result is recorded in table 6.

(embodiment 37)

Injection molding barrel temperature in process (V) is replaced with 290 DEG C, in addition to this, using same with embodiment 36 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 6.

(embodiment 38)

Injection molding barrel temperature in process (V) is replaced with 350 DEG C, in addition to this, using same with embodiment 36 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 6.

(embodiment 39)

The complex obtained using the process (IV) by embodiment 20, in addition to this, using side same as embodiment 35 Method makes test film, for each evaluation.Evaluation result is recorded in table 6.

Table 6

In embodiment 35, due to meeting process (I-2)~(III-2) and process (V), mechanical characteristic and molding are had both The productivity of cyclicity, fibre reinforced polyarylene sulfide is also excellent.

In embodiment 39, due to meeting process (I-2)~(III-2), process (IV) and process (V), mechanics is had both The productivity of characteristic and molding cycles, fibre reinforced polyarylene sulfide is also excellent.

By the comparison of embodiment 36,37,38 it is found that by process (V), by processing and forming when being injection moulded It is carried out at a temperature of temperature is low compared with temperature when obtaining complex in process (III-2), thus resulting fibre reinforced The leakage ingredient of polyarylene sulfide is reduced, and molding cycles improve.

(embodiment 40)

Using ingredient shown in table 7, condition, be related to by the one embodiment of the present invention using following step 3 manufacturing methods manufacture fibre reinforced polyarylene sulfide, are evaluated.

As process (V), the complex obtained by the process of embodiment 24 (III-3) is cut off, average grain diameter 5mm is made Particle.Using injection (mo(u)lding) machine (JSW society J150EII-P), above-mentioned particle is used to be injection moulded, to produce test Piece.Maximum pressure when being injection moulded is set as being injected by injection moulding in 300 DEG C of barrel temperature, 150 DEG C of mold temperature progress Type pressure.Evaluation result is recorded in table 7.

(embodiment 41)

The complex obtained using the process (III-3) by embodiment 25, in addition to this, using same as embodiment 40 Method makes test film, for each evaluation.Evaluation result is recorded in table 7.

(embodiment 42)

Injection molding barrel temperature in process (V) is replaced with 290 DEG C, in addition to this, using same with embodiment 41 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 7.

(embodiment 43)

Injection molding barrel temperature in process (V) is replaced with 350 DEG C, in addition to this, using same with embodiment 41 The method of sample makes test film, for each evaluation.Evaluation result is recorded in table 7.

(embodiment 44)

The complex obtained using the process (IV) by embodiment 26, in addition to this, using side same as embodiment 40 Method makes test film, for each evaluation.Evaluation result is recorded in table 7.

Table 7

In embodiment 40, due to meeting process (I-3)~(III-3) and process (V), mechanical characteristic and molding are had both The productivity of cyclicity, fibre reinforced polyarylene sulfide is also excellent.

In embodiment 44, due to meeting process (I-3)~(III-3) and process (IV) and process (V), mechanics is had both The productivity of characteristic and molding cycles, fibre reinforced polyarylene sulfide is also excellent.

By the comparison of embodiment 41,42,43 it is found that the processing and forming by process (V), when making to be injection moulded Temperature of the temperature when obtaining complex in the process (III-3) compared to it is low at a temperature of carry out, thus the increasing of resulting carbon fiber The leakage ingredient of strong polyarylene sulfide is reduced, and molding cycles improve.

Industry utilizability

In accordance with the invention it is possible to have both the productivity and mechanical characteristic and molding cycles of fibre reinforced polyarylene sulfide Property.Therefore, casting of electronic device, electric and electronic portion can be suitable for by the fibre reinforced polyarylene sulfide that the present invention obtains Part purposes, automotive part, vehicle associated components, building materials, sports goods etc..

Claims

1. a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following processes (I-1)~process (III-1),

Process (I-1): will be poly- with the above carbodiimide of at least two in 100 mass parts of polyarylene sulfide (A) and 1 molecule 0.1~10 mass parts of carbodiimide (B) are mixed, and heat simultaneously melting mixing for resulting mixture, to be melted Melt the process of mixture,

Process (II-1): will by process (I-1) obtain melting mixing object polyarylene sulfide (A) glass transition temperature with Upper and fusing point temperature below is heated, to promote the reaction of the carbodiimide in melting mixing object and obtain poly- carbon two The process of imine modified polyarylene sulfide (C-1),

Process (III-1): making poly- carbodiimide modified polyarylene sulfide (C-1) melting obtained by process (II-1), and opposite In 100 mass parts of polyarylene sulfide (A) for carbon fiber (D) Composite of 10~300 mass parts, the process for obtaining complex, and And the process (III-1) is to be impregnated in the poly- carbodiimide modified polyarylene sulfide (C-1) melted comprising carbon fiber (D) process of substrate.

2. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 1, in process (I-1), if will The time required for beginning to warm up mixture and terminating to polyarylene sulfide (A) and poly- carbodiimide (B) melting is set as t1, will be from Polyarylene sulfide (A) and poly- carbodiimide (B) melting terminate to be set as t2 to the time required for taking-up melting mixing object, then t1 < The unit of t2, t1 and t2 are all the seconds.

3. a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following processes (I-2)~process (III-2),

Process (I-2): by the poly- carbodiimide (B) in 1 molecule with the above carbodiimide of at least two in the ingredient (B) Temperature more than softening point is heated, to promote the mutual reaction of carbodiimide and obtain poly- carbodiimide reactant (B-2) process,

Process (II-2): by 100 mass parts of polyarylene sulfide (A) and poly- 0.1~10 mass of carbodiimide reactant (B-2) Part is mixed, and heat simultaneously melting mixing for resulting mixture, to obtain poly- carbodiimide modified polyarylene sulfide (C-2) process,

Process (III-2): making poly- carbodiimide modified polyarylene sulfide (C-2) melting obtained by process (II-2), and opposite In 100 mass parts of polyarylene sulfide (A) for carbon fiber (D) Composite of 10~300 mass parts, the process for obtaining complex, and And the process (III-2) is to be impregnated in the poly- carbodiimide modified polyarylene sulfide (C-2) melted comprising carbon fiber (D) process of substrate.

4. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 3, in process (I-2), ingredient (B) Softening point more than temperature be 50~250 DEG C of temperature.

5. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 3, in process (I-2), in ingredient (B) time that temperature more than softening point is heated is 1~48 hour.

6. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 4, in process (I-2), in ingredient (B) time that temperature more than softening point is heated is 1~48 hour.

7. a kind of manufacturing method of fibre reinforced polyarylene sulfide comprising following processes (I-3)~process (III-3),

Process (I-3): acquisition, which is mixed in 100 mass parts of polyarylene sulfide (A) and 1 molecule, has the above carbon two of at least two sub- The process of the mixture of 0.1~10 mass parts of poly- carbodiimide (B) of amido,

Process (II-3): temperature of the mixture obtained by process (I-3) more than the fusing point of polyarylene sulfide (A) is added Heat and melting mixing, to promote the reaction of carbodiimide and obtain the work of poly- carbodiimide modified polyarylene sulfide (C-3) Sequence,

Process (III-3): the temperature temperature below when melting mixing in process (II-3) changes the poly- carbodiimide Property polyarylene sulfide (C-3) melt, with relative to 100 mass parts of polyarylene sulfide (A) be 10~300 mass parts carbon fiber (D) Composite, the process for obtaining complex, and the process (III-3) are to keep the poly- carbodiimide modified melted poly- The process that arylene sulfide (C-3) is impregnated in the substrate comprising carbon fiber (D).

8. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 7, in process (II-3), polyarylene More than the fusing point of thioether (A) temperature is 330~400 DEG C, in process (III-3), when melting mixing in process (II-3) Temperature temperature below be 280~330 DEG C.

9. the manufacturing method of fibre reinforced polyarylene sulfide according to any one of claims 1 to 8, further in work In sequence (I-1), (II-2) or (II-3), by least part of melting mixing under -0.05MPa reduced pressure below into Row.

10. the manufacturing method of fibre reinforced polyarylene sulfide according to any one of claims 1 to 8 comprising under State process (IV): will by process (III-1), (III-2) or (III-3) obtain complex polyarylene sulfide (A) glass Change transition temperature or more and fusing point temperature below is heated, to promote the reaction of compound intracorporal carbodiimide.

11. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 10, further process (I-1), (II-2) or in (II-3), at least part of melting mixing is carried out under -0.05MPa reduced pressure below.

12. the manufacturing method of fibre reinforced polyarylene sulfide according to any one of claims 1 to 8 comprising under It states process (V): the complex obtained in process (III-1), (III-2) or (III-3) is injection moulded or is press-formed.

13. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 10 comprising following processes (V): The complex that have passed through process (IV) is injection moulded or is press-formed.

14. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 12, further process (I-1), (II-2) or in (II-3), at least part of melting mixing is carried out under -0.05MPa reduced pressure below.

15. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 13, further process (I-1), (II-2) or in (II-3), at least part of melting mixing is carried out under -0.05MPa reduced pressure below.

16. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 12 makes to be injected in process (V) In formation processing temperatures and process (III-1), (III-2) or (III-3) when molding or extrusion forming when acquisition complex Temperature is comparably low temperature.

17. the manufacturing method of fibre reinforced polyarylene sulfide according to claim 13 makes to be injected in process (V) In formation processing temperatures and process (III-1), (III-2) or (III-3) when molding or extrusion forming when acquisition complex Temperature is comparably low temperature.

18. the manufacturing method of fibre reinforced polyarylene sulfide according to any one of claims 1 to 8, carbon fiber (D) Table has been carried out with the compound (E) in 1 molecule with 3 or more at least one kind of functional groups in carboxyl, hydroxyl and epoxy group Surface treatment.